JP5477268B2 - Photosensitive resin composition and insulating film for touch panel - Google Patents

Description

  The present invention relates to a photosensitive resin composition and an insulating film for a touch panel using the same.

  In recent years, as electronic devices have become more sophisticated, diversified, and smaller and lighter, a transparent touch panel is mounted on the front surface of a display element such as a liquid crystal, and characters, symbols, patterns, etc. displayed on the display element through this transparent touch panel There are an increasing number of devices that perform visual recognition and selection, and switch each function of the device by operating a transparent touch panel.

  The touch panel is, for example, a bank ATM, a vending machine, a personal digital assistant (PDA, UMPC), a copier, a facsimile, a portable game machine, a guide board, a car navigation, a multimedia station (a multifunction terminal installed in a convenience store) ), And rapidly becoming widespread as input devices such as mobile phones, railway vehicle monitoring devices, and answering devices such as quiz programs.

Existing touch panel systems can be classified into a resistive film system, an optical system, an electrostatic capacity system, an ultrasonic system, a pressure system, an electromagnetic wave induction system, an image recognition system, a vibration detection system, and the like.
Specific examples of a touch panel arranged on a display device such as a liquid crystal include a resistance film method and a capacitance method. The resistance film method is a method of detecting a pressed position by voltage, and a capacitance method. Detects the position by capturing the change in capacitance caused by pressing.
As for the electrostatic capacity method, Patent Documents 1 to 3 and the like are disclosed, and an insulating film and a protective film are provided in the laminated structure in order to prevent erroneous recognition of a contact position.

  The performance required for this insulating film and protective film is such as adhesion to substrates, bases, and other layers (glass, inorganic material, metal material, transparent electrode such as ITO, organic material, etc.), ITO etching solution, etc. Resistance to acid (acid resistance), heat resistance in a baking process exceeding 300 ° C., and transmittance when formed into a laminated substrate are required.

  Moreover, high surface hardness is requested | required of the insulating film and protective film used for a touchscreen use, and the method of adding inorganic oxide microparticles | fine-particles to the resin component is disclosed by patent document 4. FIG. However, although such a method can provide high surface hardness and adhesiveness, it has a drawback in that it yellows after the baking process at a high temperature and the transmittance decreases. Patent Document 5 discloses a photosensitive resin composition having good radiation sensitivity, developability and storage stability by combining a photo radical polymerization system and a photo cation polymerization system. It was difficult to obtain good adhesion.

  That is, the conventional photosensitive resin composition is excellent in adhesion to the substrate, film hardness, and resistance, and cannot satisfy all of the transmittance.

JP 2008-65748 A JP 2009-15490 A JP 2010-44453 A JP 2000-281863 A JP 2010-27033 A

  An object of the present invention is a photosensitive resin composition having good adhesion to a substrate, a base, etc., high film hardness, heat resistance and acid resistance, high transmittance, and particularly high transmittance around a wavelength of 400 nm. An object is to provide an insulating film for a touch panel using the object.

As a result of intensive studies on new means that can solve the above-mentioned problems, the present inventor has found that a photosensitive resin composition containing the materials described below can solve the above-mentioned problems, leading to the present invention.
That is, the present invention relates to a resin (A) containing a resin (A1) having an ethylenically unsaturated double bond in the side chain, a photoradical polymerization initiator (B), a photocationic polymerization initiator (C), an ethylenically unsaturated group. Including saturated monomer (D), epoxy compound (E), and oxetane compound (F), the weight of ethylenically unsaturated monomer (D) is Met, the weight of epoxy compound (E) is Mce, and the oxetane compound The present invention relates to a photosensitive resin composition, wherein (Mce + Mco) / (Met + Mce + Mco) is 0.4 or more and 0.9 or less when the weight of (F) is Mco.

In the present invention, the resin (A1) having an ethylenically unsaturated double bond in the side chain is copolymerized with the following (a1), (a2) and (a3) to obtain a copolymer (a6). The copolymer (a6) and the unsaturated monobasic acid (a4) are reacted to obtain a copolymer (a7), and the obtained copolymer (a7) and a polybasic acid anhydride are obtained. It contains the resin (A1-a) obtained by reacting (a5) with the photosensitive resin composition.
(A1): Compound (a2) having an alicyclic skeleton and an unsaturated bond in one molecule; Compound (a3) having an epoxy group and an unsaturated bond in one molecule; (a1) and (a2) Compound having an unsaturated bond other than (a4); Unsaturated monobasic acid (a5); Polybasic acid anhydride

The present invention also relates to the photosensitive resin composition, wherein Mce / (Mce + Mco) is 0.4 or more and 0.95 or less.
In the present invention, when the solid content weight of the photosensitive resin composition is NV, the weight of the photo radical polymerization initiator (B) is Ir, and the weight of the photo cationic polymerization initiator (C) is Ic, (Ir + Ic) / NV is 0.01 or more and 0.15 or less, It is related with the said photosensitive resin composition characterized by the above-mentioned.
In the present invention, when the weight of the radical photopolymerization initiator (B) is Ir and the weight of the cationic photopolymerization initiator (C) is Ic, Ic / (Ir + Ic) is 0.2 or more and 0.5 or less. It is related with the said photosensitive resin composition characterized by the above-mentioned.

The present invention also relates to the photosensitive resin composition, wherein the epoxy compound (E) is a compound represented by the following formula (2-1) or formula (2-2).
Formula (2-1)

Formula (2-2)

The present invention also relates to the photosensitive resin composition, wherein the oxetane compound (F) is a compound represented by the following formula (3-1) or formula (3-5).
Formula (3-1)

Formula (3-5)

The present invention also relates to the photosensitive resin composition, wherein the photoradical polymerization initiator (B) is an acetophenone photopolymerization initiator or an oxime ester photopolymerization initiator.
In the present invention, the photoradical polymerization initiator (B) is selected from the group consisting of 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one or 1,2-octadion-1- [4- ( Phenylthio)-, 2- (o-benzoyloxime)]. The present invention relates to the photosensitive resin composition.
The present invention further includes the inorganic oxide fine particles comprising at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, indium, tin, antimony and cerium. The present invention relates to a functional resin composition.
Moreover, this invention relates to the insulating film for touchscreens formed using the said photosensitive resin composition.

  The photosensitive resin composition of the present invention has high hardness and good adhesion to a substrate and a base, and has a high transmittance, particularly a high transmittance around a wavelength of 400 nm, and an ITO etching solution (aqua regia). In addition, since it is excellent in resistance (acid resistance) to an etching solution of Metal or Metal (mixed solution of nitric acid-acetic acid-phosphoric acid), it is suitable for forming an “insulating film for a touch panel”.

First, the photosensitive resin composition of the present invention will be described.
The photosensitive resin composition of the present invention comprises a resin (A) containing a resin (A1) having an ethylenically unsaturated double bond in the side chain, a photoradical polymerization initiator (B), and a photocationic polymerization initiator (C). , Ethylenically unsaturated monomer (D), epoxy compound (E), and oxetane compound (F), the weight of ethylenically unsaturated monomer (D) is Met, the weight of epoxy compound (E) is Mce, where the weight of the oxetane compound (F) is Mco, (Mce + Mco) / (Met + Mce + Mco) is 0.4 or more and 0.9 or less.

  When the photosensitive resin composition of the present invention is irradiated with radiation, two kinds of polymerization reactions of radical polymerization of an ethylenically unsaturated double bond and cationic polymerization of an epoxy compound and an oxetane compound proceed in parallel. Since radical polymerization proceeds rapidly by irradiation with radiation, it forms a strong crosslink after exposure and greatly contributes to the hardness of the coating film. In addition, since cationic polymerization has less curing shrinkage than radical polymerization, poor adhesion due to shrinkage stress, which is a drawback of radical polymerization, is less likely to occur. By combining these two types of polymerization reactions, a cross-linking reaction proceeds after exposure to obtain a coating film with high hardness, and a coating film with little cure shrinkage and excellent adhesion to a substrate is obtained. In the photosensitive resin composition in which (Mce + Mco) / (Met + Mce + Mco) is 0.4 or more and 0.9 or less, radical polymerization and cationic polymerization proceed in a well-balanced manner, so that both hardness and adhesion are excellent. When (Mce + Mco) / (Met + Mce + Mco) is less than 0.4, the cationic polymerization reaction does not proceed efficiently, resulting in poor adhesion. When (Mce + Mco) / (Met + Mce + Mco) exceeds 0.9, the radical polymerization does not proceed sufficiently, and the coating film is weakly crosslinked after exposure, resulting in low hardness.

<Resin (A)>
The photosensitive resin composition of the present invention is characterized by containing a resin (A1) having an ethylenically unsaturated double bond in the side chain.
(Resin (A1))
The resin (A1) is not particularly limited as long as it has an ethylenically unsaturated double bond in the side chain, but among them, the main chain is preferably linear, in order to impart alkali developability. A resin having alkali solubility is more preferable. In particular, the resin (A1-a) having a specific structure is preferable because a coating film excellent in transmittance and hardness can be formed.

  Examples of the resin (A1) include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, and β-carboxyethyl (meth). Acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, penta Erythritol tri (meth) acrylate, 1,6-hexanediol diglycidyl ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl Recall diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, methylolated (meth) acrylic acid ester, epoxy (meth) acrylate, urethane acrylate Acrylic acid esters and methacrylic acid esters such as styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, acrylonitrile Of polymer compounds obtained by polymerizing monomers / oligomers such as (meth) acrylic acid and other monomers / oligomers having an acid value By reacting a reactive substituent such as an isocyanate group, an aldehyde group or an epoxy group with a reactive substituent such as an acid group, a carboxyl group or an amino group, a (meth) acrylic compound or cinnamic acid is reacted, A resin into which a photocrosslinkable group such as an acryloyl group or a styryl group is introduced is used. Further, a linear polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is converted into a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. A half-esterified product can also be used.

[Resin (A1-a)]
Among them, as the resin (A1) having an ethylenically unsaturated double bond in the side chain, the following (a1), (a2) and (a3) were copolymerized to obtain a copolymer (a6), and obtained. A copolymer (a7) is reacted with an unsaturated monobasic acid (a4) to obtain a copolymer (a7). Further, the obtained copolymers (a7) and (a5) are reacted with each other. By including the resin (A1-a) obtained, the adhesion to the substrate or the base becomes good, and a coating film having a low dielectric constant and dielectric loss tangent and good electrical characteristics can be obtained.
(A1): Compound (a2) having an alicyclic skeleton and an unsaturated bond in one molecule; Compound (a3) having an epoxy group and an unsaturated bond in one molecule; (a1) and (a2) Compound having an unsaturated bond other than (a4); Unsaturated monobasic acid (a5); Polybasic acid anhydride

  (A1); Specifically, as a compound having an alicyclic skeleton and an unsaturated bond in one molecule, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cycloheptyl (meta ) Acrylate, cyclooctyl (meth) acrylate, menthyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, dicyclopentenyloxyethyl ( (Meth) acrylate, cyclohexenyl (meth) acrylate, cycloheptenyl (meth) acrylate, cyclooctenyl (meth) acrylate, mentadienyl (meth) acrylate, isobornyl (meth) acrylate, pina Le (meth) acrylate, adamantyl (meth) acrylate, norbornenyl (meth) acrylate, derivatives having substituents pinenyl (meth) acrylate and on the alicyclic ring. Examples of the substituent on the alicyclic ring of these monomers include an alkyl group, a hydroxyl group, and a carboxyl group.

  Among them, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, dicyclo Pentenyloxyethyl (meth) acrylate is preferred, and most preferred are isobornyl (meth) acrylate, adamantyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and dicyclopentenyl (meth) acrylate. These can be used alone or in combination.

  (A2); As a compound having an unsaturated bond and an epoxy group in one molecule, glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-propylglycidyl (meth) acrylate, β-methylglycidyl- α-ethyl acrylate, 3-methyl-3,4-epoxybutyl (meth) acrylate, 4-methyl-4,5-epoxypentyl (meth) acrylate, 5-methyl-5,6-epoxyhexyl (meth) acrylate, Examples thereof include glycidyl vinyl ether, and glycidyl (meth) acrylate is preferred.

Specific examples of the compound having an unsaturated bond other than (a3); (a1) and (a2) include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-hydroxyethyl (meth). Unsubstituted or substituted alkyl esters of unsaturated carboxylic acids such as acrylates, aminoethyl (meth) acrylates;
Monosaturated carboxylic acid ester compounds of glycols such as oligoethylene glycol monoalkyl (meth) acrylates;
Ester compounds containing an aromatic ring of an unsaturated carboxylic acid such as benzyl (meth) acrylate and phenoxy (meth) acrylate;
Aromatic vinyl compounds such as styrene, α-methylstyrene, α-phenylstyrene and vinyltoluene;
Carboxylic acid vinyl esters such as vinyl acetate and vinyl propionate;
Vinyl cyanide compounds such as (meth) acrylonitrile and α-chloroacrylonitrile;
And N-substituted maleimide compounds such as N-cyclohexylmaleimide, N-phenylmaleimide, and N-benzylmaleimide. These can be used alone or in combination.

  (A4); As unsaturated monobasic acids, (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, cyano Examples thereof include monocarboxylic acids such as substituted products. Of these, (meth) acrylic acid is preferred.

  (A5); As polybasic acid anhydrides, dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride, etc .: anhydrous Examples thereof include polybasic acid anhydrides such as trimellitic acid, pyromellitic anhydride, benzophenone tetracarboxylic acid anhydride, and biphenyl tetracarboxylic acid anhydride. Of these, tetrahydrophthalic anhydride or succinic anhydride is preferred.

[Production Method of Resin (A1-a)]
Resin (A1-a) is obtained by copolymerizing (a1), (a2) and (a3) to obtain a copolymer (a6), and obtaining the copolymer (a6) and the following (a4): It is a copolymer obtained by reacting to obtain a copolymer (a7), and further reacting the obtained copolymer (a7) with a polybasic acid anhydride (a5).

First, (a1), (a2) and (a3) are copolymerized to obtain a copolymer (a6). This copolymerization is performed under normal conditions. For example, in a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introduction tube, 0.5 to 20 times based on the weight of the total amount of (a1), (a2) and (a3) An amount of solvent is introduced and the atmosphere in the flask is replaced with nitrogen from air. Then, after heating up a solvent to 40-140 degreeC, it is a mass reference | standard with respect to the predetermined amount of (a1), (a2) and (a3), and the total amount of (a1), (a2) and (a3). 0 to 20 times the amount of solvent, and a solution obtained by adding 0.1 to 10 parts of the polymerization initiator with respect to the weight ratio of (a1), (a2) and (a3) (stirred and dissolved at room temperature or under heating) Is added dropwise from the dropping funnel to the flask over 0.1 to 8 hours, and further stirred at 40 to 140 ° C. for 1 to 10 hours.
In the above step, a part or all of the polymerization initiator may be charged to the flask side,
A part or all of (a1), (a2) and (a3) may be charged to the flask side. Moreover, in order to control molecular weight and molecular weight distribution, you may use (alpha) -methylstyrene dimer and a mercapto compound as a chain transfer agent. The amount of α-methylstyrene dimer or mercapto compound used is 0.005 to 5 parts on a mass basis with respect to the total amount of (a1) to (a3). In addition, the above-described polymerization conditions may be appropriately adjusted in the preparation method and the reaction temperature in consideration of the production equipment, the amount of heat generated by the polymerization, and the like.

  The ratio of the constituent components derived from each is a molar fraction with respect to the total number of moles of the constituent components constituting the copolymer (a6), 2 to 40 mol% of the structural units derived from (a1), The structural unit derived from (a2) is preferably 2 to 95 mol%, the structural unit derived from (a3) is preferably 3 to 65 mol%, and the structural unit derived from (a1) from the balance of flexibility and heat resistance. 5 to 35 mol%, 5 to 80 mol% of structural units derived from (a2), and 15 to 50 mol% of structural units derived from (a3) are more preferable.

Next, unsaturated monobasic acid (a4) is added to the copolymer (a6) to impart light and thermosetting properties to the resin (A). The reaction of the copolymer (a6) and the unsaturated monobasic acid (a4) can be performed, for example, under the conditions described in JP-A-2001-89533. Specifically, the atmosphere in the flask is replaced with nitrogen to air, and 5 to 100 mol% of unsaturated monobasic acid (a4) in terms of mole fraction with respect to the structural unit derived from the copolymer (a6). ), As a reaction catalyst for a carboxyl group and an epoxy group, for example, trisdimethylaminomethylphenol is 0.01 to 5% on a mass basis with respect to the total amount of (a1) to (a4), and a polymerization inhibitor For example, by putting hydroquinone in a flask on the basis of mass with respect to the total amount of (a1) to (a4), 0.001 to 5% and reacting at 60 to 130 ° C. for 1 to 10 hours, The copolymer (a6) and the unsaturated monobasic acid (a4) can be reacted. Similar to the polymerization conditions, the charging method and the reaction temperature may be appropriately adjusted in consideration of the production equipment, the amount of heat generated by the polymerization, and the like.
The amount of the unsaturated monobasic acid (a4) added is 5 to 100 mol%, preferably 10 to 95 mol%, based on the epoxy group in the resin obtained by copolymerizing (a1) to (a3). is there. It is preferable that the composition ratio of (a2) is within the above range because sufficient photocurability and thermosetting can be obtained and the reliability is excellent.
Next, the copolymer (a7) and (a5) are reacted to impart alkali solubility to the resin (A).
The reaction of the copolymers (a7) and (a5) can be performed, for example, under the conditions described in JP 2001-89533 A. Specifically, 5 to 100 mol% of (a5) as a reaction catalyst, for example, as a reaction catalyst with respect to the structural unit derived from the copolymer (a7) and the unsaturated monobasic acid (a4), , By adding 0.01 to 5% of triethylamine in a flask with respect to the total amount of (a1) to (a4) in a flask and reacting at 60 to 130 ° C. for 1 to 10 hours, Copolymers (a7) and (a5) can be reacted. Similar to the polymerization conditions, the charging method and the reaction temperature may be appropriately adjusted in consideration of the production equipment, the amount of heat generated by the polymerization, and the like.
The amount of (a5) added is 5 to 100 mol%, preferably 10 to 95 mol%, based on the number of moles of the alcoholic hydroxyl group of the copolymer (a7).

The weight average molecular weight in terms of polystyrene of the resin (A1-a) is preferably 3000 to 100,000, more preferably 5000 to 50000. When the weight average molecular weight of the resin (A1-a) is in the above range, the coating property is good, the film is not easily reduced during development, and the developability of the unexposed part is good during development. And preferred.
The molecular weight distribution [weight average molecular weight / number average molecular weight] of the resin (A1-a) is preferably 1.5 to 6.0, and more preferably 1.8 to 4.0. The molecular weight distribution in the above range is preferable because the developability is excellent.

  The content of the resin (A1) used in the photosensitive resin composition of the present invention is usually 5 to 90% by weight, preferably 10 to 70% by weight, based on the solid content of the photosensitive resin composition (100% by weight). %. It is preferable for the content of the resin (A1) to be in the above-mentioned range since it is excellent in solubility in a developing solution, hardly causes a development residue, and does not easily reduce the film thickness at the exposed portion during development.

(Other resins (A2))
The resin (A) of the photosensitive resin composition of the present invention may contain other resin (A2) in addition to the resin (A1). The other resin (A2) may be a resin that does not have an ethylenically unsaturated double bond in the side chain, and may be a thermosetting resin.

<Epoxy compound (E)>
Examples of the epoxy compound (E) include known compounds, and specifically, dicyclopentadiene dioxide, limonene dioxide, 4-vinylcyclohexene dioxide, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxy. cyclohexanecarboxylate, di (3,4-epoxycyclohexyl) adipate, 1,2, 8,9 - diepoxy limonene, 3, 4-epoxycyclohexenylmethyl-3 ', 4'-epoxy cyclohexene carboxylate, bisphenol A type Epoxy resins, halogenated bisphenol A type epoxy resins, bisphenol F type epoxy resins, o-, m-, p-cresol novolak type epoxy resins, phenol novolak type epoxy resins, and the like are used.
Among these formulas (2-1), or 1,2 of the formula (2-2), 8,9 - diepoxy limonene, 3, 4-epoxycyclohexenylmethyl-3 ', 4'-epoxy cyclohexene carboxylate Is preferable in terms of hardness and adhesion. These may be used alone or in combination.

Formula (2-1)

Formula (2-2)

  The content of the epoxy compound (E) is usually 0.5 to 50% by weight, preferably 1 to 40% by weight, based on the solid content of the photosensitive resin composition (100% by weight). It is preferable that the content of the epoxy compound (E) is in the above range because a coating film having excellent hardness and adhesion can be obtained.

<Oxetane compound (F)>
Examples of the oxetane compound (F) include known compounds. Examples of the oxetane compound (F) include those in which the oxetane group is monofunctional and those in which the oxetane group is bifunctional or more. Examples of the monofunctional oxetane group include 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3- (phenoxymethyl) oxetane, 3 -Ethyl-3- (2-methacryloxymethyl) oxetane, 3-ethyl-3-{[3- (triethoxysilyl) propoxy] methyl} oxetane, and the like.

Among them, as the oxetane group is monofunctional, preferably 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane represented by the following formula (3-1) or formula (3-2), or 3 -Ethyl-3-hydroxymethyloxetane is preferred.
Formula (3-1)

Formula (3-2)

Examples of the bifunctional oxetane group include 4,4′-bis [(3-ethyl-3-oxetanyl) methoxymethyl] biphenyl (for example, OXBP manufactured by Ube Industries, Ltd.), 1,4-bis [(3- Ethyl-3-oxetanyl) methoxymethyl] benzene (for example, Ube Industries, Ltd., OXTP), 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene (for example, Toagosei Co., Ltd., OXT-121), di [1-ethyl (3-oxetanyl)] methyl ether (for example, OXT-221, manufactured by Toagosei Co., Ltd.) and the like, preferably the following general formula (3-3):
General formula (3-3)

[In Formula (3-3), R ² may be the same or different, and is a hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or 1 to 10 carbon atoms. Represents a hydroxyalkylene group. R ³ represents a divalent organic group having 1 to 30 carbon atoms. n ¹ is an integer of from 1 to 20. ] Is preferable.
The number of carbon atoms of R ² is more preferably 1 to 4, further preferably 1 or 2, and particularly preferably 1.

Among these, the following general formula (3-4) is preferable.
Formula (3-4)

n ² is preferably represented by an integer of 1 to 10.

  Further, examples of the oxetane compound (F) include silsesquioxanes having an oxetane group such as oxetanylsilsesquioxane.

Specific examples include di [1-ethyl (3-oxetanyl)] methyl ether of the following formula (3-5) , 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3- (2-ethylhexyloxymethyl). ) oxetane, 3-ethyl-3- (2-phenoxymethyl) oxetane, 1,4-bis {[(3-ethyl Le - 3 - oxetanyl) methoxy] methyl} benzene, di [1-ethyl (3-oxetanyl) ] Methyl ether etc. are mentioned.
Formula (3-5)

  Among oxetane compounds (F), in particular 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane of formula (3-1) or di [1-ethyl (3-oxetanyl) of formula (3-5) Methyl ether is preferred because of its high hardness. These may be used alone or in combination.

  The content of the oxetane compound (F) used in the photosensitive resin composition of the present invention is usually 0.5 to 50% by weight, preferably 1 based on the solid content of the photosensitive resin composition (100% by weight). -40% by weight. It is preferable that the content of the oxetane compound (F) is in the above range because the hardness is high and an excellent coating film can be obtained.

Further, when the weights of the epoxy compound (E) and the oxetane compound (F) contained in the photosensitive resin composition are Mce and Mco, Mce / (Mce + Mco) is 0.4 or more and 0.95 or less. Preferably, it is 0.5 or more and 0.9 or less.
When Mce / (Mce + Mco) is less than 0.4, the composition has few epoxy compounds with excellent adhesion, resulting in poor adhesion. On the other hand, when Mce / (Mce + Mco) exceeds 0.95, the composition has few oxetane compounds having excellent hardness, and the hardness becomes low.

<Ethylenically unsaturated monomer (D)>
The photosensitive resin composition of the present invention contains an ethylenically unsaturated monomer (D). As the ethylenically unsaturated monomer (D), bifunctional and other polyfunctional monomers can be used in addition to monofunctional monomers.
Specific examples of the monofunctional monomer include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, N-vinyl pyrrolidone, and the like.
Specific examples of the bifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 3- And methylpentanediol di (meth) acrylate.
Specific examples of other polyfunctional monomers include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexa (meth) acrylate. And caprolactone-modified dipentaerythritol hexaacrylate, a reaction product of pentaerythritol tri (meth) acrylate and an acid anhydride, a reaction product of dipentaerythritol penta (meth) acrylate and an acid anhydride, and the like.
From the viewpoint of transmittance, dipentaerythritol pentaacrylate, dipentaerythritol hexa (meth) acrylate, and caprolactone-modified dipentaerythritol hexaacrylate are preferable. Among these, caprolactone-modified dipentaerythritol hexaacrylate is particularly preferred because it can impart heat resistance and adhesion while maintaining transmittance.
The content of the ethylenically unsaturated monomer (D) is preferably 5 to 50% by weight in a total of 100% by weight of the solid content of the photosensitive resin composition.

<Photoradical polymerization initiator (B)>
Examples of the photo radical polymerization initiator (B) include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1- ON, 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2- Acetophenone photopolymerization initiators such as morpholinopropan-1-one, 1,2-octadion-1- [4- (phenylthio)-, 2- (o-benzoyloxime)], ethanone, 1- [9-ethyl -6- (2-Methylbenzoyl) -9H-carbazol-3-yl]-, 1- (o-acetyloxy ) Oxime ester photopolymerization initiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyl dimethyl ketal and other benzoin photopolymerization initiators, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4- Benzophenone photopolymerization initiators such as phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2 Thioxanthone photopolymerization initiators such as 2,4-diisopropylthioxanthone, 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2 -Piperonyl-4,6-bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (Trichloromethyl) -s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6 Triazine photopolymerization initiators such as triazine and 2,4-trichloromethyl (4′-methoxystyryl) -6-triazine, borate photopolymerization initiators, carbazole photopolymerization initiators Imidazole-based photopolymerization initiator, or the like are used.

Among them, acetophenone photopolymerization initiators and oxime ester photopolymerization initiators are preferable because they have high sensitivity and can be added in a small amount, so that the transmittance increases.
Among acetophenone photopolymerization initiators and oxime ester photopolymerization initiators, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 1 , 2-octadion-1- [4- (phenylthio)-, 2- (o-benzoyloxime)], especially 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, , 2-octadion-1- [4- (phenylthio)-, 2- (o-benzoyloxime)] has a high transmittance as an insulating film because it does not turn yellow during the heating step, and particularly has a transmittance around 400 nm. This is more preferable because a photosensitive resin composition having a high value can be provided. These may be used alone or in combination.
The radical photopolymerization initiator (B) is preferably used in an amount of 1 to 30% by weight in a total of 100% by weight of the solid content of the photosensitive resin composition, and an amount of 1 to 10% by weight from the viewpoint of transmittance. It is more preferable to use in.

The radical photopolymerization initiator (B) is used singly or in combination of two or more. As the sensitizer, α-acyloxy ester, acyl phosphine oxide, methyl phenylglyoxylate, benzyl, 9,10-phenol are used. Nanthrenequinone, camphorquinone, ethylanthraquinone, 4,4′-diethylisophthalophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 4,4′-diethylaminobenzophenone, etc. These compounds can also be used in combination.
The sensitizer can be used in an amount of 0.1 to 150 parts by weight with respect to 100 parts by weight of the radical photopolymerization initiator (B).

<Photocationic polymerization initiator (C)>
Examples of the cationic photopolymerization initiator (C) include metal fluoroboron complex salts and trifluorinated boron complex compounds such as those described in US Pat. No. 3,379,653; bis (perfluorocarbons) as described in US Pat. No. 3,586,616. Alkylsulfonyl) methane metal salts; aryldiazonium compounds as described in US Pat. No. 3,708,296; aromatic onium salts of Group VIa elements as described in US Pat. No. 4,058,400; Aromatic onium salts of group Va elements as described; dicarbonyl chelates of group IIIa to Va elements as described in US Pat. No. 4068091; thiopyrylium as described in US Pat. No. 4,139,655 Salt; described in US Pat. No. 4,161,478 MF ₆ like being ^- anion (where M is phosphorus, are selected from antimony and arsenic) VIb element in the form of; arylsulfonium salts as described in U.S. Pat. No. 4,231,951; the U.S. Patent 4,256,828 Aromatic iodonium complex salts and aromatic sulfonium complex salts as described in US Pat. R. Bis [4- (Di) as described by Watt et al. In "Journal of Polymer Science, Polymer Chemistry", Vol. 22, paragraph 1789 (1984). Ferrylsulfonio) phenyl] sulfide-bis-hexafluorometal salts (eg, phosphates, arsenates, antimonates, etc.); mixed ligand metal salts of iron compounds; silanol-aluminum complexes; . These compounds are also referred to as ultraviolet polymerization initiators. These cationic photopolymerization initiators (C) may be used alone or in combination of two or more.

  Among the photocationic polymerization initiators (C), arylsulfonium complex salts, aromatic iodonium complex salts of halogen-containing complex ions or aromatic sulfonium complex salts, and aromatic onium salts of Group II, Group V and Group VI elements are preferred.

  The cationic photopolymerization initiator (C) is preferably used in an amount of 0.1 to 30% by weight in a total of 100% by weight of the solid content of the photosensitive resin composition, and 1 to 20 from the viewpoint of sensitivity and transmittance. More preferably, it is used in an amount of% by weight.

  When the weight of the photo radical polymerization initiator (B) contained in the total solid weight (NV) of the photosensitive resin composition is Ir and the weight of the photo cationic polymerization initiator (C) is Ic, (Ir + Ic) / NV is preferably 0.01 or more and 0.15 or less, and more preferably 0.02 or more and 0.12 or less. When (Ir + Ic) / NV is less than 0.01, crosslinking after radiation exposure is weak and the hardness of the coating film is lowered, which is not preferable. When (Ir + Ic) / NV exceeds 0.15, the coloration derived from the polymerization initiator becomes conspicuous and the transmittance decreases, which is not preferable.

  Further, when the weight of the photo radical polymerization initiator (B) contained in the solid content of the photosensitive resin composition is Ir and the weight of the photo cationic polymerization initiator (C) is Ic, Ic / (Ir + Ic) is 0. It is preferably 2 or more and 0.5 or less, and more preferably 0.25 or more and 0.45 or less. When Ic / (Ir + Ic) is less than 0.2, radical polymerization is more likely to proceed than cationic polymerization, curing shrinkage is promoted, and adhesion is deteriorated due to shrinkage stress. When Ic / (Ir + Ic) exceeds 0.5, the contribution of radical polymerization decreases and the hardness decreases.

<Inorganic oxide fine particles>
The photosensitive resin composition of the present invention preferably contains inorganic oxide fine particles. The inorganic oxide fine particles are formed of at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, indium, tin, antimony, and cerium, from the viewpoint of the colorlessness of the cured film of the resulting curable composition. Oxide particles are preferred. Of these, from the viewpoint of transmittance, oxide particles of silicon, zirconium, or aluminum are preferable, and silicon oxide particles are particularly preferable. By using the resin (A1) and the inorganic oxide fine particles, the hardness can be increased and a coating film having a high transmittance can be obtained.

  Inorganic oxide fine particles are used in physical dispersions such as plasma discharge treatment and corona discharge treatment in order to stabilize dispersion in the dispersion or coating solution, or to improve the affinity and binding to the binder component. Surface treatment, chemical surface treatment with a surfactant, a coupling agent, or the like may be performed.

  The average primary particle diameter of the oxide particles is preferably 1 nm to 1000 nm, more preferably 3 nm to 100 nm, and particularly preferably 5 nm to 30 nm. When the average primary particle diameter exceeds 1000 nm, the transparency when cured is reduced, or the surface state when coated is liable to deteriorate. Various surfactants and amines may be added to improve the dispersibility of the particles.

  The average primary particle diameter of the inorganic oxide fine particles is measured using, for example, the BET method. Specifically, the specific surface area of the inorganic oxide fine particles obtained by the BET method is obtained, the ratio of volume to surface area is calculated using the specific gravity of the inorganic oxide, and the particles are assumed to be true spheres. There is a method of obtaining the particle diameter from these ratios to obtain the average primary particle diameter.

  The inorganic oxide particles are preferably used as an organic solvent dispersion. When used as an organic solvent dispersion, the dispersion medium is preferably an organic solvent from the viewpoint of compatibility with other components and dispersibility. Examples of such an organic solvent include alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethyl acetate, butyl acetate, ethyl lactate, and γ-butyrolactone , Esters such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; ethers such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; aromatic hydrocarbons such as benzene, toluene and xylene; dimethylformamide, dimethylacetamide, Examples thereof include amides such as N-methylpyrrolidone. Of these, methanol, isopropanol, butanol, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, toluene and xylene are preferred.

  Commercially available products as silicon oxide fine particle dispersions particularly preferably used in the present invention include MA-ST-MS, IPA-ST, IPA-ST-MS, IPA-ST- manufactured by Nissan Chemical Industries, Ltd. L, IPA-ST-ZL, IPA-ST-UP, EG-ST, NPC-ST-30, MEK-ST, MEK-ST-L, MIBK-ST, NBA-ST, XBA-ST, DMAC-ST, ST-UP, ST-OUP, ST-20, ST-40, ST-C, ST-N, ST-O, ST-50, ST-OL, etc., hollow silica CS60-IPA manufactured by Catalyst Kasei Kogyo Co., Ltd., etc. Can be mentioned. As the powdered silica, Aerosil 130, Aerosil 300, Aerosil 380, Aerosil TT600, Aerosil OX50, Silex H31, H32, H51, H52, H121, H122, Asahi Glass Co., Ltd., Nippon Silica Industry, Nippon Aerosil Co., Ltd. Examples include E220A and E220 manufactured by Fuji Electric, SYLYSIA470 manufactured by Fuji Silysia Co., Ltd., SG flake manufactured by Nippon Sheet Glass Co., Ltd., and the like.

  Examples of products that are commercially available as zirconia oxide fine particle dispersions preferably used in the present invention include ZR-40BL, ZR-30BS, ZR-30AL, ZR-30AH manufactured by Nissan Chemical Industries, Ltd., Sumitomo Osaka Cement ( HXU-110JC manufactured by Co., Ltd. can be mentioned.

  Commercially available products as aluminum oxide fine particle dispersions preferably used in the present invention include alumina sol-100, alumina sol-200, alumina sol-520 manufactured by Nissan Chemical Industries, Ltd. and AS- manufactured by Sumitomo Osaka Cement Co., Ltd. 150I, AS-150T.

  In addition, inorganic oxide fine particle dispersions preferably used in the present invention are shown below. Antimony oxide fine particle dispersions include Celnax CX-Z330H manufactured by Nissan Chemical Industries, Ltd., and oxide fine particle dispersions of aluminum, titanium, tin, indium, zinc, etc. be able to.

  The addition amount of the inorganic oxide fine particles is preferably 10% by weight to 40% by weight, and more preferably 20% by weight to 35% by weight, in the total solid content of 100% by weight in the photosensitive composition. When the addition amount is less than 10% by weight, it is difficult to obtain effects such as improvement in pencil hardness and acid resistance. On the other hand, when the addition amount exceeds 40% by weight, there is a problem that adhesion is lowered.

<Adhesion promoting additive>
The photosensitive resin composition of the present invention is preferable because it further contains an adhesion promoting additive to improve adhesion with a glass substrate, ITO and the like.
Adhesion promoting additives include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycid Xylpropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxy Silane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3- Minopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1, 3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, 3-ureidopropyltriethoxy Examples include silane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, and 3-isocyanatopropyltriethoxysilane. .
Among these, inclusion of a silane-based additive is preferable because adhesion to a glass substrate or ITO is improved, and 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxy are preferable. Silane is particularly preferred.
The adhesion promoting additive is preferably used in an amount of 0.1 to 10% by weight in a total of 100% by weight of the solid content of the photosensitive resin composition. If the amount is less than 0.1% by weight from the viewpoint of adhesion, the adhesion improving effect is difficult to obtain because the amount of the adhesion promoting additive is small, and if it exceeds 10% by weight, the resin in the photosensitive resin composition or ethylenic unsaturation Since monomers, photopolymerization initiators and the like are relatively decreased, characteristics such as adhesion and hardness are deteriorated.

<Other ingredients>
In the photosensitive resin composition of the present invention, a solvent, a surfactant, a storage stabilizer, a leveling agent and the like can be used as necessary.

(solvent)
Examples of the solvent include 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, and 2-methyl. -1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene N, N-dimethylacetamide, N, N-dimethylformamide, n-butylal N-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, Ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether Ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol Monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, cyclopentanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl acetate Dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene Glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol Methyl isobutyl ketone, methyl cyclohexanol, acetic acid n- amyl acetate n- butyl, isoamyl acetate, isobutyl acetate, propyl acetate, include dibasic acid esters such as, used these alone or in mixtures.

In consideration of the drying property of the solvent, it is preferable to include a high boiling point solvent of 160 ° C. or higher in die coating or printing methods. For example, 3-methoxy-3-methyl-1-butanol (bp 174 ° C.), 1, 3 -Butanediol (bp 203 ° C.), 3-methyl-1,3-butanediol (bp 203 ° C.), 2-methyl-1,3-propanediol (bp 213 ° C.), diisobutyl ketone (bp 168.1 ° C.), ethylene glycol mono Butyl ether (bp 171.2 ° C.), ethylene glycol monohexyl ether (bp 208.1 ° C.), ethylene glycol monobutyl ether acetate (bp 191.5 ° C.), ethylene glycol dibutyl ether (bp 203.3 ° C.), diethylene glycol monomethyl ether (bp 194.0) ℃), Diechi Glycol monoethyl ether (bp 202.0 ° C.), diethylene glycol diethyl ether (bp 188.4 ° C.), diethylene glycol monoisopropyl ether (bp 207.3 ° C.), propylene glycol monobutyl ether (bp 170.2 ° C.), propylene glycol diacetate (bp 190 0.0 ° C.), dipropylene glycol monomethyl ether (bp 187.2 ° C.), dipropylene glycol monoethyl ether (bp 197.8 ° C.), dipropylene glycol monopropyl ether (bp 212.0 ° C.), dipropylene glycol dimethyl ether (bp 175 ° C.) ), Tripropylene glycol monomethyl ether (bp 206.3 ° C.), ethyl 3-ethoxypropionate (bp 169.7 ° C.), 3-methoxybutene Ruacetate (bp 172.5 ° C.), 3-methoxy-3-methylbutyl acetate (bp 188 ° C.), γ-butyrolactone (bp 204 ° C.), N, N-dimethylacetamide (bp 166.1 ° C.), N-methylpyrrolidone (bp 202 ° C), p-chlorotoluene (bp162.0 ° C), o-diethylbenzene (bp183.4 ° C), m-diethylbenzene (bp181.1 ° C), p-diethylbenzene (bp183.8 ° C), o-dichlorobenzene (bp180) 0.5 ° C), m-dichlorobenzene (bp 173.0 ° C), n-butylbenzene (bp183.3 ° C), sec-butylbenzene (bp178.3 ° C), tert-butylbenzene (bp169.1 ° C), cyclo Hexanol (bp 161.1 ° C), cyclohexyl acetate (bp 73 ° C.), include such methylcyclohexanol (bp174 ℃), preferably high-boiling solvent or 160 ° C. 5 to 50 wt% based on the total amount of solvent.
The solvent can be used in an amount of 200 to 4000 parts by weight with respect to 100 parts by weight of the total solid content.

(Storage stabilizer)
Examples of the storage stabilizer include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and organic acids such as methyl ether, t-butylpyrocatechol, triethylphosphine, and triphenylphosphine. Examples thereof include phosphine and phosphite. The storage stabilizer can be used in an amount of 0.1 to 5 parts by weight in a total of 100 parts by weight of the photosensitive resin composition.

(Leveling agent)
In order to improve the leveling property of the composition on the transparent substrate, it is preferable to add a leveling agent to the colored composition of the present invention. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning, BYK-330 manufactured by BYK Chemie. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK Chemie. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can be used in combination. In general, the leveling agent content is preferably 0.003 to 0.5% by weight based on 100% by weight of the total amount of the photosensitive resin composition.

  Particularly preferred as a leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, having a hydrophilic group but low solubility in water, and when added to a coloring composition, It has the characteristics of low surface tension reduction ability, and it is useful to have good wettability to the glass plate despite its low surface tension reduction ability. Those that can sufficiently suppress the chargeability can be preferably used. As a leveling agent having such preferable characteristics, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. Examples of the polyalkylene oxide unit include a polyethylene oxide unit and a polypropylene oxide unit, and dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

  In addition, the bonding form of the polyalkylene oxide unit with dimethylpolysiloxane includes a pendant type in which the polyalkylene oxide unit is bonded in the repeating unit of dimethylpolysiloxane, a terminal-modified type in which the end of dimethylpolysiloxane is bonded, and dimethylpolysiloxane. Any of linear block copolymer types in which they are alternately and repeatedly bonded may be used. Dimethylpolysiloxane having a polyalkylene oxide unit is commercially available from Toray Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ. -2207, but is not limited thereto.

An anionic, cationic, nonionic or amphoteric surfactant can be supplementarily added to the leveling agent. Two or more kinds of surfactants may be mixed and used.
Anionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, alkyl diphenyl ether disulfonic acid Sodium, lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Examples include esters.

  Examples of the chaotic surfactant that is supplementarily added to the leveling agent include alkyl quaternary ammonium salts and their ethylene oxide adducts. Nonionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate And amphoteric surfactants such as alkyl dimethylamino acetic acid betaine and alkylimidazolines, and fluorine-based and silicone-based surfactants.

<Production method of photosensitive resin composition>
The photosensitive resin composition of the present invention comprises a resin (A) containing a resin (A1) having an ethylenically unsaturated double bond in the side chain, a photoradical polymerization initiator (B), and a photocationic polymerization initiator (C). The ethylenically unsaturated monomer (D), the epoxy compound (E), the oxetane compound (F), a solvent, and the like can be obtained by stirring and mixing.
The photosensitive resin composition of the present invention is a coarse particle having a size of 5 μm or more, preferably a coarse particle having a size of 1 μm or more, more preferably a coarse particle having a size of 0.5 μm or more, by means of centrifugation, sintered filter, membrane filter or the like. It is preferable to remove the mixed dust and foreign matter.

<Insulating film for touch panel>
The photosensitive resin composition according to the present invention can be applied to a glass substrate, ITO, metal film, organic film, etc. by spin coating such as spin coating, casting coating such as die coating, coating by roll coating, coating by roll transfer method, etc. To form a coating film.
Moreover, the photosensitive resin composition of this invention may be used for any of an insulating film use, a protective film use, and a flat film use, and also in each use, it may be patterned by photolithography.

  Hereinafter, the present invention will be described by way of examples. In the examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively.

Prior to the examples, the weight average molecular weight of the resin and the method for measuring the acid value will be described.
(Weight average molecular weight of resin)
It measured by polystyrene conversion using the gel permeation chromatograph measuring apparatus ("Shodex GPC System-21H" Showa Denko make).

(Acid value)
80 ml of acetone and 10 ml of water are added to 0.5 to 1 g of the resin solution and stirred to dissolve uniformly, and an automatic titrator ("COM-555" manufactured by Hiranuma Sangyo Co., Ltd.) is used with a 0.1 mol / L KOH aqueous solution as a titrant. ) And the acid value of the resin solution was measured. Then, the acid value per solid content of the resin was calculated from the acid value of the resin solution and the solid content concentration of the resin solution.

Then, the manufacturing method of resin (A1) solution and other resin (A2) solutions is demonstrated.
<Method for Producing Resin (A1) Solution>
(Preparation of resin solution (A1-1))
Place 100 parts of propylene glycol monomethyl ether acetate in a reaction vessel equipped with a thermometer, cooling tube, nitrogen gas inlet tube and stirrer in a separable four-necked flask, and heat to 120 ° C while injecting nitrogen gas into the vessel. A mixture of 5.2 parts of styrene, 35.5 parts of glycidyl methacrylate, 41.0 parts of dicyclopentanyl methacrylate, and 1.0 part of azobisisobutyronitrile was dropped over 2.5 hours from the dropping tube at a temperature to polymerize. Reaction was performed.
Next, the inside of the flask was purged with air, 0.3 parts of trisdimethylaminomethylphenol and 0.3 part of hydroquinone were added to 17.0 parts of acrylic acid, and the reaction was continued at 120 ° C. for 5 hours. The reaction was terminated when it reached 0.8, and a resin solution having a weight average molecular weight of about 12000 (measured by GPC) was obtained.
Further, 30.4 parts of tetrahydrophthalic anhydride and 0.5 part of triethylamine were added and reacted at 120 ° C. for 4 hours, and propylene glycol monomethyl ether acetate was added so that the non-volatile content was 20 % to obtain a resin solution (A1-1). Was prepared.

(Preparation of resin solution (A1-2))
A resin solution (A1-2) was prepared by performing a synthetic reaction in the same manner as the resin solution (A1-1) except that dicyclopentanyl methacrylate in the resin solution (A1-1) was changed to dicyclopentenyl methacrylate. . The weight average molecular weight was 12500.

(Preparation of resin solution (A1-3))
A synthetic reaction is performed in the same manner as the resin solution (A1-1) except that dicyclopentanyl methacrylate in the resin solution (A1-1) is changed to dicyclopentanyloxyethyl methacrylate, and the resin solution (A1-3) Was prepared. The weight average molecular weight was 12500.

(Preparation of resin solution (A1-4))
A synthetic reaction is performed in the same manner as the resin solution (A1-1) except that the dicyclopentanyl methacrylate in the resin solution (A1-1) is changed to dicyclopentenyloxyethyl methacrylate, and the resin solution (A1-4) is obtained. Prepared. The weight average molecular weight was 12500.

(Preparation of resin solution (A1-5))
370 parts of PGMEA was charged into a separable four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe and a stirring device, heated to 80 ° C., and the atmosphere in the flask was replaced with nitrogen. 18 parts of phenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toa Gosei Co., Ltd.), 10 parts of benzyl methacrylate, 18.2 parts of glycidyl methacrylate, 25 parts of methyl methacrylate, and 2.0 parts of 2,2′-azobisisobutyronitrile Was added dropwise over 2 hours. After dropping, the reaction was further carried out at 100 ° C. for 3 hours, and then 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 100 ° C. for 1 hour. Next, the inside of the container was replaced with air, 0.5 parts of trisdimethylaminophenol and 0.1 part of hydroquinone were added to 9.3 parts of acrylic acid (equivalent of glycidyl group), and 6 parts at 120 ° C. The reaction was continued for a period of time, and the reaction was terminated when the acid value of the solid content reached 0.5 to obtain an acrylic resin solution. Further, 19.5 parts of tetrahydrophthalic anhydride (equivalent of generated hydroxyl group) and 0.5 parts of triethylamine were added and reacted at 120 ° C. for 3.5 hours to obtain an acrylic resin solution.
After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and PGMEA was added to the previously synthesized resin solution so that the nonvolatile content was 20 wt%. An acrylic resin solution (A1-5) was prepared. The weight average molecular weight (Mw) was 19000.

<Method for producing other resin (A2) solution>
(Preparation of resin solution (A2-1))
70.0 parts of PGMEA was charged into a separable four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe and a stirrer, and the temperature was raised to 80 ° C. 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, 7.4 parts of paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.) A mixture of 0.4 part of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropping, the reaction was further continued for 3 hours to obtain an acrylic resin solution having a solid content of 30% by weight and a weight average molecular weight of 26000.
After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and PGMEA was added to the previously synthesized resin solution so that the nonvolatile content was 20 wt%. An acrylic resin solution (A2-1) was prepared.

[Examples 1-31, Comparative Examples 1-7]
The compositions shown in Tables 1 and 2 and the mixture of the blended amounts were stirred and mixed so as to be uniform, and then filtered through a 1 μm filter, and the photosensitivities corresponding to Examples 1 to 31 and Comparative Examples 1 to 7, respectively. Resin compositions 1 to 38 (R1 to R38) were obtained. Weight Ir of photoradical polymerization initiator (B) contained in R1 to R38, weight Ic of photocationic polymerization initiator weight (C), weight Met of ethylenically unsaturated monomer (D), epoxy compound Tables 1 and 2 show parameters calculated from the weight Mce of (E) and the weight Mco of the oxetane compound (F).

<Inorganic oxide fine particles>
ZR-40BL (Nissan Chemical Co., Ltd.); tetramethylammonium hydroxide dispersion of fine zirconia oxide particles (solid content 40%)
PMA-ST (manufactured by Nissan Chemical Co., Ltd.); PGMEA dispersion of silicon oxide fine particles (solid content 30%)
<< ethylenically unsaturated monomer (D) >>
・ DPCA30; Kayacure DPCA30 (manufactured by Nippon Kayaku Co., Ltd.)
Caprolactone-modified dipentaerythritol hexaacrylate << Epoxy compound (E) >>
· Celloxide 3000 (Daicel Chemical Industries, Ltd.): 1,2, 8,9 - diepoxy limonene, Celloxide 2021P (manufactured by Daicel Chemical Industries, Ltd.): 3, 4-epoxycyclohexenylmethyl-3 ', 4'-epoxy cyclohexene Carboxylate << Oxetane Compound (F) >>
Aron oxetane OXT-212 (manufactured by Toagosei Co., Ltd.): 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane Aron oxetane OXT-221 (manufactured by Toagosei Co., Ltd.): di [1-ethyl (3-oxetanyl) )] Methyl ether / Aron oxetane OXT-101 (manufactured by Toagosei Co., Ltd.): 3-ethyl - 3-hydroxymethyloxetane << adhesion promoting additive >>
KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.); 3-glycidoxypropyltrimethoxysilane

<< Photocationic polymerization initiator (C) >>
CPI-110P (manufactured by San Apro); diphenyl-4- (phenylthio) phenylsulfonium hexafluorophosphate << photo radical polymerization initiator (B) >>
Irgacure OXE-01 (manufactured by Ciba Japan); 1,2-octadione-1- [4- (phenylthio)-, 2- (o-benzoyloxime)]
Irgacure 184 (manufactured by Ciba Japan); 1-hydroxycyclohexyl phenyl ketone Irgacure 907 (manufactured by Ciba Japan); 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one Irgacure 369 (Ciba Japan); 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one Irgacure OXE-02 (Ciba Japan); Ethanone, 1 -[9-Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (o-acetyloxime)
Adeka Arcles N-1414: 3,6-bis (2-methyl-2-morpholinopropionyl) -9-n-octylcarbazole

《Leveling agent》
-BYK-330 2% (manufactured by Big Chemie); polyether structure-containing dimethylsiloxane PGMEA solution (adjusted to 1% solids)
"solvent"
-PGMEA: Propylene glycol monomethyl ether acetate-EEP: Ethyl 3-ethoxypropionate

<Evaluation of photosensitive resin composition>
The photosensitive resin compositions (R1 to R38) were evaluated by the evaluation methods shown below. The results are shown in Tables 1 and 2.
(Measurement of transmittance and evaluation of sensitivity)
The film thickness after finishing the photosensitive resin composition (R1 to R38) on a 100 mm × 100 mm, 0.7 mm thick glass substrate (Corning Glass Eagle 2000) at 230 ° C. for 20 minutes using a spin coater is 2 A substrate coated to a thickness of 0.0 μm was obtained. Next, after drying under reduced pressure, ultraviolet exposure was performed using an ultrahigh pressure mercury lamp at an illuminance of 20 mW / _cm ² and an exposure amount of 50 mJ / _cm ² . The coated substrate was heated at 230 ° C. for 20 minutes and allowed to cool, and then the transmittance at a wavelength of 400 nm of the obtained coating film was determined using a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.). The film thickness was measured with a stylus type film thickness meter DECTAC-3 manufactured by ULVAC.
○: Transmittance 97% or more: Good level Δ; Transmittance 95% or more and less than 97%: Inferior to ○, but practical level ×; Transmittance less than 95%: Level not suitable for practical use

(Measurement of transmittance after additional baking)
A photosensitive resin composition-coated substrate obtained by the same method as that prepared for transmittance measurement was heated at 250 ° C. for 60 minutes, allowed to cool, and then used with a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optics). The transmittance of the obtained coating film at a wavelength of 400 nm was determined.
○: Transmittance 97% or more: Good level Δ; Transmittance 95% or more and less than 97%: Inferior to ○, but practical level ×; Transmittance less than 95%: Level not suitable for practical use

(Measurement of glass adhesion and adhesion to ITO)
The adhesiveness of the coating film was evaluated by an adhesion (cross-cut method) test according to JIS K5600-5-6 on the photosensitive resin composition-coated substrate obtained by the same method as that prepared for the measurement of transmittance. The number of peels in 25 grids was counted.
The substrate used was Corning Glass Eagle 2000 and Santo Vacuum Industry ITO film.
○: Number of cross-cuts less than 2 Δ; Number of cross-cuts peeled 2 to 10 ×: Number of cross-cuts greater than 10

(Measurement of pencil hardness)
The surface hardness of the insulating film was measured by a scratch hardness (pencil method) test according to JIS K5600-5-4 for the photosensitive resin composition-coated substrate obtained by the same method as that prepared for transmittance measurement. When this value is 4H or higher, the surface hardness is good. When the hardness is 3H, the minimum practical hardness, 2H or less is not suitable for practical use.
○: 4H or more Δ; 3H
×: 2H or less

(Adhesion after acid resistance)
A substrate obtained by the same method as that prepared for transmittance measurement was immersed in aqua regia (nitric acid: hydrochloric acid = 1/3) at room temperature for 5 minutes, washed with pure water, and left for 48 hours. The substrate thus obtained was evaluated for adhesion of the coating film by an adhesion (cross-cut method) test according to JIS K5600-5-6, and the number of peels in 25 grids was counted.
○: Number of cross-cuts less than 2 Δ; Number of cross-cuts peeled 2 to 10 ×: Number of cross-cuts greater than 10

(Film hardness after acid resistance)
A substrate obtained by the same method as that prepared for transmittance measurement was immersed in aqua regia (nitric acid: hydrochloric acid = 1/3) at room temperature for 5 minutes, washed with pure water, and left for 48 hours. With respect to the substrate thus obtained, the surface hardness of the insulating film was measured by a scratch hardness (pencil method) test according to JIS K5600-5-4. When this value is 4H or higher, the surface hardness is good. When the hardness is 3H, the minimum practical hardness, 2H or less is not suitable for practical use.
○: 4H or more Δ; 3H
×: 2H or less

  As shown in Tables 1 and 2, the resin (A1), photoradical polymerization initiator (B), photocationic polymerization initiator (C), ethylenically unsaturated monomer (D), and epoxy compound, which are features of the present invention (E) and an oxetane compound (F), the weight of the ethylenically unsaturated monomer (D) is Met, the weight of the epoxy compound (E) is Mce, and the weight of the oxetane compound (F) is Mco. The photosensitive resin compositions R1 to 31 having (Mce + Mco) / (Met + Mce + Mco) of 0.4 or more and 0.9 or less are all good or practical in transmittance, acid resistance, adhesion, and pencil hardness. The result was no.

  Moreover, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one or 1,2-octadion-1- [4- (phenylthio)-, 2- (o-) is used as a radical polymerization initiator. The photosensitive resin composition using benzoyloxime)] has a particularly high transmittance.

  When Examples 10, 11, and 12 were compared, Examples 11 and 12 containing inorganic oxide fine particles had better hardness than Example 10 not containing inorganic oxide fine particles. In addition, the photosensitive resin composition of Example 12 in which the oxide fine particles were silicon had particularly good transmittance, acid resistance, adhesion, and pencil hardness.

  Further, when the adhesion promoting additive 3-glycidoxypropyltrimethoxysilane was used, the adhesion was excellent.

The resin composition of Comparative Example 1 that did not contain the epoxy compound (E) and the oxetane compound (F) and the resin composition of Comparative Example 2 that did not contain the oxetane compound (F) resulted in poor adhesion. The resin composition of Comparative Example 3 that does not contain an epoxy compound (E), the radical photopolymerization initiator (B), and the resin composition of Comparative Example 4 that does not contain an ethylenically unsaturated monomer (D) have poor hardness. As a result. Moreover, the transmittance | permeability was also low in the resin composition of the comparative example 4. The resin composition of Comparative Example 5 in which (Mce + Mco) / (Met + Mce + Mco) was less than 0.4 resulted in poor adhesion. The resin composition of Comparative Example 6 in which (Mce + Mco) / (Met + Mce + Mco) exceeded 0.9 resulted in poor hardness and adhesion.
For the resin compositions of Comparative Examples 1, 2, 5, and 6, the acid resistance was also poor.
Moreover, in the resin composition of Comparative Example 7 not containing the resin (A1), the transmittance after additional baking was low and the acid resistance was poor. Moreover, the tendency which is bad also about adhesiveness was seen.

Claims (8)

  Resin (A) containing resin (A1) having an ethylenically unsaturated double bond in the side chain, photo radical polymerization initiator (B), photo cationic polymerization initiator (C), ethylenically unsaturated monomer (D ), An epoxy compound (E), and an oxetane compound (F), the weight of the ethylenically unsaturated monomer (D) is Met, the weight of the epoxy compound (E) is Mce, and the weight of the oxetane compound (F) is (Mce + Mco) / (Met + Mce + Mco) is 0.4 or more and 0.9 or less, where Mco is a photosensitive resin composition. The resin (A1) having an ethylenically unsaturated double bond in the side chain is copolymerized with the following (a1), (a2) and (a3) to obtain a copolymer (a6). The copolymer (a6) and the unsaturated monobasic acid (a4) are reacted to obtain a copolymer (a7), and the obtained copolymer (a7) and the polybasic acid anhydride (a5) are further reacted. The photosensitive resin composition according to claim 1, comprising a resin (A1-a) obtained by heating.
(A1): Compound (a2) having an alicyclic skeleton and an unsaturated bond in one molecule; Compound (a3) having an epoxy group and an unsaturated bond in one molecule; (a1) and (a2) Compound having an unsaturated bond other than (a4); Unsaturated monobasic acid (a5); Polybasic acid anhydride When the solid content weight of the photosensitive resin composition is NV, the weight of the photoradical polymerization initiator (B) is Ir, and the weight of the photocationic polymerization initiator (C) is Ic, (Ir + Ic) / NV is 0.00. It is 01 or more and 0.15 or less, The photosensitive resin composition of Claim 1 or 2 characterized by the above-mentioned. Mce / (Mce + Mco) The photosensitive resin composition according to 1, wherein any one of claims 1 to 3, characterized in that 0.4 to 0.95.   When the weight of the photo radical polymerization initiator (B) is Ir and the weight of the photo cationic polymerization initiator (C) is Ic, Ic / (Ir + Ic) is 0.2 to 0.5. The photosensitive resin composition according to any one of claims 1 to 4. The photosensitive resin composition according to any one of claims 1 to 5, wherein the radical photopolymerization initiator (B) is an acetophenone-based photopolymerization initiator or an oxime ester-based photopolymerization initiator. Further, silicon, aluminum, zirconium, titanium, zinc, indium, tin, any one of claims 1 to 6, characterized in that it comprises at least inorganic oxide fine particles comprising one element selected from the group consisting of antimony and cerium 1 The photosensitive resin composition according to item. The photosensitive resin composition for a touch panel insulating film formed by using the according to any one of claims 1-7.