JP6577176B2 - Negative photosensitive resin composition and transfer material - Google Patents

Description

  The present invention relates to a negative photosensitive resin composition and the like.

  In recent years, touch panels have attracted attention with the spread of smartphones and tablet terminals. One of the problems with this touch panel is the deterioration of the appearance of the terminal due to the visual recognition of the pattern of Indium Tin Oxide used for sensor formation, that is, indium tin oxide (hereinafter “ITO”), that is, the problem of ITO pattern visibility. It is done.

  Recently, there has been an increasing demand for lighter and thinner terminals. For example, a method of reducing the number of glasses by forming a sensor on the back side of a cover glass has been studied. This method is called a cover glass integrated type. However, in this method, the distance from the outermost surface of the terminal to the ITO pattern is shorter than in the conventional sensor glass / cover glass separation method, and the problem of ITO pattern visibility becomes more prominent.

  As a typical technique for reducing the pattern visibility of ITO, a technique for reducing interface reflection by forming an insulating layer thin film on the upper or lower part of ITO has been developed. As a method for forming an insulating layer thin film on top of ITO, for example, as described in Patent Document 1, an alkali development type insulating film having a refractive index of 1.60 to 1.78 is applied onto ITO by spin coating, and then ITO is applied. There has been proposed a method for reducing the pattern visibility by reducing the difference in refractive index between the two. Patent Document 2 proposes a transfer sheet including an insulating film having a refractive index of 1.67 to 1.77.

Japanese Patent No. 5338701 JP 2014-71306 A

  However, for the insulating layer thin film described in Patent Document 1 and the insulating film described in Patent Document 2, metal fine particles such as zirconia are introduced into the composition in order to achieve a high refractive index. There was a problem that the adhesiveness with could not be maintained sufficiently.

  Accordingly, the problem to be solved by the present invention is a negative photosensitivity that is excellent in pattern workability and adhesion to a substrate such as an ITO substrate, has a refractive index of 1.60 or more, and is capable of alkali development. It is providing the resin composition and the transfer material containing this photosensitive resin composition.

The present inventors have found that the above problems can be solved by the following invention.
[1]
(A) a resin having an acidic functional group;
(B) a compound having an ethylenically unsaturated double bond;
(C) a photopolymerization initiator; and (D) a heteropolyacid;
A negative photosensitive resin composition comprising:
[2]
The negative photosensitive resin composition according to [1], wherein the acidic functional group of the resin having the acidic functional group (A) is a carboxyl group.
[3]
The negative photosensitive resin composition according to [1] or [2], wherein the content of the (D) heteropolyacid is 40% by mass or more based on the total solid content of the negative photosensitive composition.
[4]
The content of the resin having the acidic functional group (A) is 15% by mass to 30% by mass with respect to the total solid content of the negative photosensitive composition, and (B) the ethylenically unsaturated double bond. [3], wherein the content of the compound having a content of 10 to 20% by mass and the content of the (C) photopolymerization initiator is 0.1 to 5.0% by mass. Negative photosensitive resin composition.
[5]
The negative photosensitive resin composition according to any one of [1] to [4], which is used for protecting a wiring.
[6]
The negative photosensitive resin composition according to [5], wherein the wiring is a transparent electrode.
[7]
The negative photosensitive resin composition according to [5] or [6], wherein the wiring is formed on a flexible substrate.
[8]
[1] A transfer material in which at least one layer made of the negative photosensitive resin composition according to any one of [1] to [4] is formed on a support film.
[9]
The pattern formation method including the process of laminating | transferring the transfer material as described in [8] to a base material, exposing and developing, and forming a pattern.
[10]
The pattern forming method according to [9], further including a step of heating the pattern.
[11]
Laminating the transfer material according to [8] on a substrate, exposing and developing to form a pattern;
The pattern with heating, obtaining a heat treatment pattern; and further by exposing the heat treatment pattern at an exposure amount of 200 mJ ^/ cm 2 to 500 mJ / cm ^2, and / or is heat treatment A step of further heating the pattern at a temperature of 100 ° C. to 300 ° C. to obtain a cured product;
A cured product production method comprising:
[12]
Hardened | cured material obtained by the hardened | cured material manufacturing method as described in [11].
[13]
A touch panel display device having the cured product according to [12].

  According to the present invention, a negative photosensitive resin composition having excellent pattern processability and adhesion to a substrate such as an ITO substrate, having a refractive index of 1.60 or more, and capable of alkali development, the photosensitive property A transfer material containing a resin composition, a pattern forming method using the transfer material or a cured product production method, a cured product obtained by the cured product production method, a touch panel display device including the cured product, and the like can be provided.

  Hereinafter, the best mode for carrying out the present invention (hereinafter abbreviated as “embodiment”) will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.

<Negative photosensitive resin composition>
The negative photosensitive resin composition of the present embodiment includes (A) a resin having an acidic functional group, (B) a compound having an ethylenically unsaturated double bond, (C) a photopolymerization initiator, and (D) a heteropolyethylene. Contains acid. Optionally, the negative photosensitive resin composition may include (E) other components.

  The negative photosensitive resin composition of this embodiment can be used to protect the wiring. In that case, the protected wiring is preferably a transparent electrode and / or the protected wiring is preferably formed on a flexible substrate.

  The components (A) to (E) contained in the negative photosensitive resin composition will be described below.

<(A) Resin having an acidic functional group>
(A) The resin having an acidic functional group is not limited as long as it contains a carboxyl group, a phenolic hydroxyl group, and a sulfonic acid group, but (A) the acidic functional group of the resin having an acidic functional group is a carboxyl group. It is preferable that (A) As a resin having an acidic functional group, a vinyl resin having a carboxyl group can be suitably used.

  The vinyl-based resin having a carboxyl group is a copolymer comprising a structural unit derived from at least one of the first monomers described later and a structural unit derived from at least one of the second monomers described later. It is preferably a coalescence.

  The first monomer is a carboxylic acid or acid anhydride having one polymerizable unsaturated group in the molecule. Examples of the first monomer include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, and maleic acid half ester. Among these, (meth) acrylic acid is particularly preferable. Here, (meth) acryl indicates acryl and / or methacryl (the same applies hereinafter).

  The second monomer is a monomer that is non-acidic and has at least one polymerizable unsaturated group and at least one phenyl group that may have a substituent in the molecule. Examples of the second monomer include benzyl (meth) acrylate, styrene, and derivatives thereof.

  A third monomer can be further copolymerized with the vinyl resin having a carboxyl group. The third monomer is a non-acidic monomer and has at least one polymerizable unsaturated group in the molecule. Examples of the third monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate. , Tert-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, vinyl alcohol esters (for example, vinyl acetate), (meta ) Acrylonitrile and the like. Among these, methyl (meth) acrylate, n-butyl (meth) acrylate, or ethyl (meth) acrylate is preferable.

  The copolymerization ratio of each monomer is 10% to 25% by mass for the first monomer and 25% to 90% for the second monomer, based on the total mass of all monomers. It is preferable that the third monomer is 0 to 65% by mass, more preferably the first monomer is 15% to 20% by mass, and the second monomer is Is 40 mass% to 90 mass%, and the third monomer is 0 to 45 mass%.

  (A) The resin having an acidic functional group may be a compound obtained by reacting an epoxy resin with an unsaturated carboxylic acid and an acid anhydride. In this case, in the compound, the epoxy resin is a bisphenol F type epoxy resin, a bisphenol A type epoxy resin or a cresol novolac type epoxy resin, the unsaturated carboxylic acid is acrylic acid or methacrylic acid, and the acid anhydride is anhydrous. A compound that is succinic acid or tetrahydrophthalic anhydride is preferred. Specifically, (A) the resin having an acidic functional group may be a carboxyl group pendant unsaturated epoxy ester resin.

  Examples of commercially available carboxyl group pendant type unsaturated epoxy ester resins include ZFR-1533H (manufactured by Nippon Kayaku Co., Ltd., reaction product of bisphenol F type epoxy resin, acrylic acid, and tetrahydrophthalic anhydride), ZAR -2000 (manufactured by Nippon Kayaku Co., Ltd., reaction product of bisphenol A type epoxy resin, acrylic acid and succinic anhydride), PR-300PG (manufactured by Showa Denko KK, cresol novolac type epoxy resin, acrylic acid, and Acid anhydride reaction product) and the like.

  Furthermore, (A) the resin having an acidic functional group may have a fluorene skeleton from the viewpoint of achieving a high refractive index of the cured product, and in that case, as the resin having (A) an acidic functional group, For example, a resin containing a carboxyl group and a fluorene skeleton exemplified in JP-A-2001-354735 can be used.

  Examples of commercially available resins containing a carboxyl group and a fluorene skeleton include Denacol FCA-293 (manufactured by Nagase ChemteX Corporation).

  One type of the resin having the acidic functional group (A) described above may be used, or a plurality of types may be used in combination.

  (A) It is preferable that the weight average molecular weight of resin which has an acidic functional group is 5,000 or more and 500,000 or less. (A) The weight average molecular weight of the resin having an acidic functional group is 5,000 or more from the viewpoint of the properties of the developed aggregate, the properties of the unexposed film such as the edge fuse property and the cut chip property when used as a transfer sheet. Preferably, it is preferably 500,000 or less from the viewpoint of improving alkali solubility and image formability.

  Here, the edge fuse property is a phenomenon in which the photosensitive resin composition layer protrudes from the end face of the roll when the photosensitive resin laminate is wound into a roll. The cut chip property is a phenomenon that the chip flies when the unexposed film is cut with a cutter, and when the chip adheres to the upper surface of the photosensitive resin laminate, it is transferred to a mask in a later exposure process. It causes a defect.

  (A) The weight average molecular weight of the resin having an acidic functional group is more preferably 5,000 or more and 300,000 or less, and still more preferably 10,000 or more and 200,000 or less. The weight average molecular weight was measured by Gel Permeation Chromatography (GPC) manufactured by JASCO Corporation (pump: Gulliver, PU-1580 type, column: Shodex (registered trademark) manufactured by Showa Denko KK (KF-807, KF-806M). , KF-806M, KF-802.5) in series, moving bed solvent: tetrahydrofuran, polystyrene standard sample (using a calibration curve by Shodex STANDARD SM-105 manufactured by Showa Denko KK) as polystyrene conversion It is done.

  (A) The content of the resin having an acidic functional group is preferably 40% by mass or less from the viewpoint of refractive index when the solid content of the negative photosensitive resin composition is 100% by mass, and is alkali-soluble. And it is preferable that it is 10 mass% or more from a viewpoint of edge fuse property. (A) Content of resin which has an acidic functional group More preferably, it is 15 mass%-30 mass%.

<(B) Compound having an ethylenically unsaturated double bond>
The negative photosensitive resin composition of this embodiment is (B) a photopolymerizable compound having two or more photopolymerizable unsaturated double bonds in the molecule as a compound having an ethylenically unsaturated double bond. It is preferable to contain.

  Examples of the photopolymerizable compound having two or more photopolymerizable unsaturated double bonds in the molecule include tricyclodecane dimethylol diacrylate, ethylene oxide (EO) modified bisphenol A di (meth) acrylate, and EO modified. Hydrogenated bisphenol A di (meth) acrylate, 1,6-hexanediol (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 2 -Di (p-hydroxyphenyl) propane di (meth) acrylate, glycerol tri (meth) acrylate, trimethylolpropane EO modified tri (meth) acrylate, trimethylolpropane PO modified tri (meth) acrylate, polyoxy Ropil trimethylolpropane tri (meth) acrylate, polyoxyethyltrimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, trimethylolpropane triglycidyl ether (meth) acrylate, bisphenol A diglycidyl ether di ( (Meth) acrylate, β-hydroxypropyl-β ′-(acryloyloxy) -propyl phthalate, phenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) Acrylate, pentaerythritol tri / tetra (meth) acrylate, (meth) acrylate with fluorene skeleton Such as theft and the like.

  Among them, EO-modified bisphenol A di (meth) acrylate and / or polyethylene glycol di (meth) acrylate is preferable from the viewpoint of heat laminating properties of the photosensitive resin composition, and triglyceride is preferable from the viewpoint of chemical resistance or moisture resistance. Methylolpropane PO-modified tri (meth) acrylate is preferable, and (meth) acrylate having a fluorene skeleton is preferable from the viewpoint of achieving high refractive index of the cured product.

  One type of the compound (B) having an ethylenically unsaturated double bond described above may be used, or a plurality of types may be used in combination.

  (B) The content of the compound having an ethylenically unsaturated double bond is 5% by mass from the viewpoint of thermal laminating property or image forming property when the solid content of the negative photosensitive resin composition is 100% by mass. -30% by mass is preferable, and 10% by mass to 20% by mass is more preferable.

<(C) Photopolymerization initiator>
(C) As the photopolymerization initiator, for example, benzophenone, N, N, N ′, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone), N, N, N ′, N′-tetraethyl- 4,4′-diaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- Aromatic ketones such as (methylthio) phenyl] -2-morpholino-propanone-1 (Irgacure 907 manufactured by BASF); benzoin ether compounds such as benzoin methyl ether, benzoin ethyl ether and benzoin phenyl ether; benzoin, methyl benzoin and ethyl benzoin A benzoin compound of Etanone, 1- [9-ethyl-6 -(2-Methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), 1- [4- (phenylthio) phenyl] -3-cyclopentylpropane-1,2-dione-2 Oxime ester compounds such as-(O-benzoyloxime) (TR-PBG-305, product name manufactured by Nikko Chemtech Co., Ltd.); 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5' -Lophine dimer such as tetraphenyl-1,2'-biimidazole; benzyl derivative such as benzyldimethyl ketal; acridine derivative such as 9-phenylacridine, 1,7-bis (9,9'-acridinyl) heptane; N-phenylglycine derivatives such as N-phenylglycine; coumarin compounds; oxazole compounds; and 2,4,6-trimethylbenzoyl-diphe Le - phosphine oxide compounds such as phosphine oxide.

  Among these, aromatic ketones, oxime ester compounds, phosphine oxide compounds from the viewpoints of transparency of the protective film formed, sensitivity of the photosensitive resin composition or photosensitive resin laminate, and storage stability of the composition film Or a combination of lophine dimer and N-phenylglycine is preferred.

  (C) Content of a photoinitiator is 0.1 mass%-10 mass% from a viewpoint of image forming property, when the solid content of a negative photosensitive resin composition is 100 mass%. Preferably, it is 0.1 mass%-5.0 mass%, More preferably, it is 0.5 mass%-5.0 mass%.

<(D) Heteropoly acid>
In general, a heteropolyacid refers to an (X ₁ M _m O _n ) ^x- type polyacid in which a hetero atom is inserted into a metal oxyacid skeleton with respect to an isopoly acid (M _m O _n ) ^x- The (D) heteropolyacid contained in the negative photosensitive resin composition of the present embodiment is composed of tungstic acid composed of tungsten trioxide (WO ₃ ) and / or molybdenum trioxide (MoO ₃ ). it is intended to include molybdate. These can be dissolved in various organic solvents such as methanol, ethanol, acetone and methyl ethyl ketone. These may be used alone or in combination.

  The negative photosensitive resin composition of this embodiment comprises (A) a resin having an acidic functional group, (B) a compound having an ethylenically unsaturated double bond, and (C) a photopolymerization initiator. By including an acid, when a transfer material is formed from a negative photosensitive resin composition, it is excellent in low temperature laminating properties, pattern workability, adhesion to a substrate such as an ITO substrate, and the like.

  (D) The content of the heteropolyacid may be 10 to 80% by mass when the solid content of the negative photosensitive resin composition is 100% by mass, but the refractive index of the negative photosensitive resin composition is 1. It is preferably 40% by mass or more from the viewpoint of increasing to 60 or more, and preferably 60% by mass or less from the viewpoint of thermal laminating property or image forming property.

<(E) Other ingredients>
The negative photosensitive resin composition of this embodiment is a group consisting of a triazole compound, a thiadiazole compound, and a tetrazole compound as (E) other components from the viewpoint of imparting rust prevention to the negative photosensitive resin composition. You may further contain the at least 1 sort (s) of rust preventive agent selected more.

  Examples of the triazole compound include mercapto groups such as benzotriazole, 1H-benzotriazole-1-acetonitrile, benzotriazole-5-carboxylic acid, 1H-benzotriazole-1-methanol, carboxybenzotriazole, and 3-mercaptotriazole. Triazole compounds containing: Triazole compounds containing an amino group such as 3-amino-5-mercaptotriazole.

  Examples of the thiadiazole compound include 2-amino-5-mercapto-1,3,4-thiadiazole, 2,1,3-benzothiadiazole and the like.

  Examples of the tetrazole compounds include 1H-tetrazole, 5-amino-1H-tetrazole, 5-methyl-1H-tetrazole, 1-methyl-5-ethyl-tetrazole, 1-methyl-5-mercapto-tetrazole, 1- And carboxymethyl-5-mercapto-tetrazole.

  The content of the rust inhibitor in the negative photosensitive resin composition of the present embodiment is 0.05% by mass to 10.0% by mass when the solid content of the negative photosensitive resin composition is 100% by mass. It is preferable that it is 0.1 mass%-2.0 mass%, and it is still more preferable that it is 0.2 mass%-1.0 mass%. By adjusting the content of the rust preventive agent within the above range, the effect of improving the corrosion resistance of the electrode or the adhesion to the metal electrode can be sufficiently obtained while suppressing problems such as deterioration in developability or resolution. be able to.

  Further, in order to improve the thermal stability or storage stability of the negative photosensitive resin composition, the negative photosensitive resin composition comprises (E) other components such as a radical polymerization inhibitor, benzotriazoles, and One or more compounds selected from the group consisting of carboxybenzotriazoles may be further contained.

  Examples of the radical polymerization inhibitor include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, 2,6-di-tert-butyl-p-cresol, 2,2′-methylenebis. (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), nitrosophenylhydroxyamine aluminum salt, diphenylnitrosamine and the like. As benzotriazoles or carboxybenzotriazoles, compounds known in the art may be used.

<Transfer material>
A transfer material can be obtained by forming at least one layer comprising the negative photosensitive resin composition of the present embodiment on a temporary support. The transfer material of the present embodiment has a temporary support and an alkali-developable photosensitive resin layer formed on the temporary support, and has a wavelength of 633 nm after curing of the alkali-developable photosensitive resin layer. The refractive index is 1.60 or more.

  The transfer material of this embodiment can improve the visibility of a transparent electrode pattern by using it for an electrostatic capacitance type input device by the above structures, and can improve the performance of an electrostatic capacitance type input device. By reducing the difference in refractive index between a transparent electrode pattern (for example, ITO) having a refractive index of 1.60 or more and the transparent curable resin layer, light reflection is reduced and the transparent electrode pattern becomes difficult to see, improving visibility. can do.

  Hereinafter, the transfer material of this embodiment will be described. The transfer material of this embodiment is preferably for a transparent insulating layer or a transparent protective layer of a touch panel input device.

  The transfer material of the present embodiment includes a temporary support. As the temporary support, a material that is flexible and does not cause significant deformation, shrinkage, or elongation under pressure or under pressure and heating can be used. The temporary support may be in the form of a support film.

  Examples of the temporary support include, for example, polyethylene terephthalate film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, polyvinylidene chloride film, vinylidene chloride copolymer film, polymethyl methacrylate copolymer film, polystyrene film. , A polyacrylonitrile film, a styrene copolymer film, a polyamide film, a cellulose derivative film, and the like. Among them, a biaxially stretched polyethylene terephthalate film is particularly preferable.

  The thinner the film, the more advantageous in terms of image formation and economy, but it is preferably 10 to 30 μm in order to maintain the strength.

  The transfer material of this embodiment may optionally have a protective layer. The protective layer may be in the form of a film. An important characteristic of the protective film used for the transfer material is that the protective film is sufficiently smaller than the support film in terms of adhesion to the photosensitive resin layer and can be easily peeled off. For example, a polyethylene film and / or a polypropylene film can be preferably used as the protective film. Also, a film having excellent peelability disclosed in JP-A-59-202457 can be used. The thickness of the protective layer is preferably 10 to 100 μm, and more preferably 10 to 50 μm.

  The film thickness of the photosensitive resin layer used for the transfer material is preferably 0.05 μm or more or 3 μm or more from the viewpoint of following the unevenness of the wiring and ensuring rust prevention, and has transparency and flexibility. From the viewpoint, it is preferably 10 μm or less. The film thickness of the photosensitive resin layer is preferably 0.05 to 5.0 μm from the viewpoint of improving the visibility of the transparent electrode.

  A known method can be adopted as a method for preparing a transfer material by sequentially laminating a support film, a photosensitive resin layer, and, if necessary, a protective layer. For example, the photosensitive resin composition used for the photosensitive resin layer is mixed with a solvent that dissolves the photosensitive resin composition into a uniform solution, first applied onto the support film using a bar coater or roll coater, and then dried to form the support film. A photosensitive resin layer made of a photosensitive resin composition can be laminated thereon.

  Next, if necessary, a photosensitive resin laminate can be produced by laminating a protective layer on the photosensitive resin layer.

  Examples of the solvent that dissolves the photosensitive resin composition include ketones typified by methyl ethyl ketone (MEK), alcohols typified by methanol, ethanol, and isopropanol. It is preferable to add the said solvent to the photosensitive resin composition so that the viscosity of the solution of the photosensitive resin composition apply | coated on a support film may be 10-4000 mPa * s at 25 degreeC.

  In addition, the photosensitive resin composition according to the present application can be laminated together with a transparent electrode protecting photosensitive resin composition having a refractive index of less than 1.60 and used as a transfer material having a layer structure of two or more layers.

  The transfer material having a layer structure of two or more layers is first coated with a transparent electrode protecting photosensitive resin composition solution having a refractive index of less than 1.60 on a support and dried, and then the photosensitive material of this embodiment is used. A sequential coating method in which a functional resin composition solution is applied and dried, a method in which a resin composition solution of each layer is extruded from a multilayer die and simultaneously applied and then dried, or after each layer is formed on a support, respectively It can be obtained by thermocompression bonding.

<Pattern formation method>
The transfer material including the photosensitive resin layer of the present embodiment can be used for forming a pattern. The pattern includes a laminating step of laminating the transfer material of the present embodiment on a base material, an exposure step of exposing the photosensitive resin laminate included in the laminated transfer material, and a developing for developing the exposed photosensitive resin laminate. It can be formed by a pattern forming method including a process.

  When the transfer material is used as a wiring protective film, the pattern forming method includes a step of further exposing the obtained pattern and / or a heat treatment of the obtained pattern in addition to the laminating step, the exposing step and the developing step. It is preferable to include a process.

  Hereinafter, a specific example of the pattern forming method will be shown.

  Examples of the substrate include a copper-clad laminate for the production of a printed wiring board, and a glass substrate such as a substrate for a plasma display panel or a surface electrolytic display substrate for the production of an uneven substrate. Furthermore, organic EL sealing cap base materials, silicon wafers having through holes formed therein, ceramic base materials, and the like can be given.

  The substrate for plasma display is obtained by forming an electrode on glass, applying a dielectric layer, then applying a partition glass paste, and subjecting the partition glass paste to sandblasting to form a partition. It is a glass substrate. Those obtained by subjecting these glass substrates to sand blasting are uneven substrates. As the substrate for the wiring protective film, use a substrate in which wiring is formed on a flexible copper-clad laminate, a glass substrate, a touch panel sensor substrate in which a transparent electrode or a metal electrode is formed on a transparent resin substrate, and the like. Can do.

  The flexible copper-clad laminate or the base material for touch panel electrode formation is a base material obtained by laminating copper or ITO on a flexible film.

  As said film, the film which consists of polyimide, polyester, etc. is mentioned, for example. The thickness of the film is preferably 10 μm to 100 μm.

  By performing the laminating process on the base material as described above, the photosensitive resin layer of the present embodiment is formed on the copper or ITO layer of the base material. When the transfer material has a protective film, the protective film is peeled off, and then the transfer material is heat-pressed and laminated on the substrate surface with a laminator. In this case, the transfer material may be laminated only on one side of the substrate surface or on both sides. The heating temperature at this time is generally about 40 ° C. to about 160 ° C.

  Next, exposure is performed using an exposure machine. If necessary, the support film is peeled off and exposed to active light through a photomask. The exposure amount is determined by the light source illuminance and the exposure time. The exposure amount may be measured using a light meter. Examples of the exposure machine include a scattered light exposure machine using an ultra-high pressure mercury lamp as a light source, a parallel light exposure machine with the same degree of parallelism, and a proximity exposure machine with a gap between the mask and the workpiece. Furthermore, a projection type exposure machine with a mask to image size ratio of 1: 1, a reduction projection exposure machine called a high illumination stepper (registered trademark), or an exposure machine using a concave mirror called a mirror projection aligner (registered trademark). Can be mentioned.

  In the exposure step, a direct drawing exposure method may be used. Direct drawing exposure is a method in which exposure is performed by directly drawing on a substrate without using a photomask. As the light source, for example, a solid laser having a wavelength of 350 nm to 410 nm, a semiconductor laser, or an ultrahigh pressure mercury lamp is used. The drawing pattern is controlled by a computer, and the exposure amount in this case is determined by the light source illuminance and the moving speed of the substrate.

Next, a developing process is performed using a developing device. After the exposure, if there is a support film on the photosensitive resin layer, this is removed if necessary, and then the unexposed portion is developed and removed using a developer of an alkaline aqueous solution to obtain a resist image. As the alkaline aqueous solution, an aqueous solution of Na ₂ CO ₃ or K ₂ CO ₃ is used. The alkaline aqueous solution is appropriately selected according to the characteristics of the photosensitive resin layer, but a Na ₂ CO ₃ aqueous solution having a concentration of about 0.2% by mass to about 2% by mass and a temperature of about 20 ° C. to about 40 ° C. is generally used. Can be used. A surface active agent, an antifoaming agent, a small amount of an organic solvent for promoting development, and the like may be mixed in the alkaline aqueous solution. In consideration of the influence on the substrate, an amine-based alkaline aqueous solution such as a tetraammonium hydroxide (TMAH) aqueous solution can also be used. The concentration of the alkaline aqueous solution can be appropriately selected according to the development speed. From the viewpoints of low odor, excellent handleability, and simple management and post-treatment, an aqueous solution of Na ₂ CO _{3 of} 1% by mass and 30 ° C. is preferred.

<Hardened product manufacturing method, cured product>
A cured product can be obtained by the pattern forming method described above. The obtained cured product may be in the form of, for example, a film or a film. It is also preferable that the obtained cured product is mounted on a touch panel display device.

In order to use the cured product as a wiring protective film, the cured product production method of the present embodiment includes the following steps:
(I) a step of laminating the transfer material of the present embodiment on a substrate, exposing and developing to form a pattern;
(Ii) the pattern with heating, to obtain a heat-treated patterning process; and (iii) by a heat treatment pattern further exposure at an exposure amount of 200 mJ ^/ cm 2 to 500 mJ / cm ^2, and / Or a step of further heating the heat-treated pattern at a temperature of 100 ° C. to 300 ° C. to obtain a cured product;
It is preferable to contain.

  The step (i) can be performed in the same manner as the laminating step, the exposing step and the developing step described for the pattern forming method. The step (ii) can be performed in the same manner as the heating step described for the pattern forming method.

It is preferable to carry out the step (iii) since the chemical resistance of the cured product can be further improved. Exposure in step (iii) may be performed in the same manner as the exposure step as described for the pattern forming ^method, but preferably carried out at an exposure dose of ^{200mJ / cm 2 ~500mJ / cm 2} . For the heating in the step (iii), a heating furnace of an appropriate system such as hot air, infrared rays, far infrared rays or the like can be used.

  Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited thereto.

1. Production and Evaluation of Single Layer Transfer Film The single layer transfer films in Examples 1 to 8 and Comparative Example 1 were produced as follows.

<Production of single-layer transfer film>
Methyl ethyl ketone (MEK) is added to the photosensitive resin composition having the composition shown in the following Table 1 (however, the number of each component indicates the blending amount (part by mass) as the solid content) to a solid content concentration of 20% by mass. The mixture was sufficiently stirred and mixed to obtain a photosensitive resin composition preparation.

  Using a blade coater, uniformly apply the photosensitive resin composition preparation liquid to the surface of a 16 μm-thick polyethylene terephthalate (PET) film (Toray Industries, Inc., FB40), which is a support film, in a 95 ° C. dryer. And dried for 3 minutes to form a uniform photosensitive resin layer on the support film. The thickness of the photosensitive resin layer was 2 μm.

  Next, a 12 μm-thick polypropylene film was bonded as a protective film on the surface of the photosensitive resin layer to obtain a laminate of the photosensitive resin composition. Table 2 shows the names of the material components in the photosensitive resin composition preparation liquid represented by abbreviations in Table 1.

<Refractive index measurement>
The single layer transfer film was exposed with a scattered light exposure machine (HMW-201KB, manufactured by Oak Seisakusho Co., Ltd.) with an exposure amount of 500 mJ / cm ² . At this time, light was irradiated from the PET surface side of the single-layer transfer film. Thereafter, the protective film was peeled off, and a curing treatment was performed at 145 ° C. for 30 minutes to obtain a sample. Refractive index measurement was performed using the sample. For the measurement of the refractive index, a prism coupler (laser refractive index measurement model 2010, laser beam wavelength: 633 nm) manufactured by Metricon Corporation was used.

2.2 Production and Evaluation of Layer Transfer Film The two-layer transfer film in Examples 1 to 8 and Comparative Example 1 is a transfer film composed of a photosensitive resin layer (a) and a photosensitive resin layer (b). It was produced by a coating method.

<Production of two-layer transfer film>
[Photosensitive resin layer (a)]
A 50% by mass MEK solution of a composition containing the following components in the following proportions was prepared.
A copolymer having a composition of methacrylic acid / benzyl methacrylate (polymerization ratio 20/80), an acid equivalent of 430, and a weight average molecular weight of 50,000: 35 parts by mass. Methacrylic acid / benzyl methacrylate A copolymer having a composition of (polymerization ratio 15/85), an acid equivalent of 573, and a weight average molecular weight of 50,000: 15 parts by mass Trimethylolpropane trimethacrylate (manufactured by Arkema Co., Ltd.) SR-350FF, product name) ... 10 parts by mass, nonabutylene glycol diacrylate (Shin-Nakamura Chemical Co., Ltd. A-PTMG-65, product name) ... 15 parts by mass, both ends of bisphenol A Polyethylene glycol dimethacrylate with an average of 2 moles of ethylene oxide added to each (PDBE-200A manufactured by NOF Corporation, product name) 15 parts by weight of 1- [4- (phenylthio) phenyl] -3-cyclopentyl-1,2-dione-2-(o-benzoyl oxime)
(Nikko Chemtech Co., Ltd. TR-PBG-305, product name) ... 0.6 parts by mass, 5-benzotriazolecarboxylic acid ... 0.2 parts by mass, aluminum added with 3 mol of nitrosophenylhydroxylamine Salt: 0.005 parts by mass

  The 50% by mass MEK solution was uniformly applied to the surface of a 16 μm thick PET film (Toray Industries, FB40) as a support film using a blade coater and dried in a 95 ° C. dryer for 3 minutes. Then, the uniform photosensitive resin layer (a) was formed on the support film. The thickness of the photosensitive resin layer (a) was 5 μm, and the refractive index measured by the above-described refractive index measurement method was 1.54.

[Photosensitive resin layer (b), two-layer transfer film]
Next, a 1% by mass MEK solution of a photosensitive resin composition having the composition shown in Table 1 was prepared. This 1% by mass MEK solution was uniformly applied to the surface of the photosensitive resin layer (a) formed on the above support film using a blade coater, and dried in a 95 ° C. dryer for 3 minutes. Then, a uniform photosensitive resin layer (b) is formed on the support film, and a 12 μm-thick polypropylene film is bonded as a protective film on the surface of the photosensitive resin layer (b) to form the photosensitive resin layer (a) and the photosensitive film. A transfer film composed of two layers of the conductive resin layer (b) was obtained. As a result of carrying out SEM observation of the cross section of the photosensitive resin layer (b), the thickness of the photosensitive resin layer (b) was 0.1 μm.

<Image formation evaluation>
The protective film of the two-layer transfer film is peeled off, and a roll temperature of 100 ° C. to 170 ° C., an air pressure of 0.4 MPa, and a laminating speed of 1 are applied to a copper-clad laminate by a hot roll laminator (VA-400III, manufactured by Taisei Laminator Co., Ltd.). Lamination was performed under the condition of 0.0 m / min. The laminated substrate was exposed and developed with a line pattern in which the width of the exposed area and the unexposed area was 1: 1.

  The exposure is carried out through a photomask necessary for the evaluation of the photosensitive resin layer through the PET film as a support, and an exposure using a super high pressure mercury lamp (HMW-801 manufactured by Oak Manufacturing Co., Ltd.) to form a 21-step tablet made by Stöffer in 5 steps. Done in quantity.

In the development, after peeling off the PET film, a 1 mass% Na ₂ CO ₃ aqueous solution at 30 ° C. is sprayed for a predetermined time using an alkali developing machine (produced by Fuji Kiko Co., Ltd., a dry film developing machine). The unexposed portion of the resin layer was dissolved and removed in a time twice the minimum image time. The minimum image time is the shortest time required for the unexposed portion of the photosensitive resin layer to completely dissolve. The minimum mask width in which the pattern was normally formed after development was taken as the resolution value. Image formability was evaluated according to the following criteria.
○: When the resolution value is 100 μm or less ×: When the resolution value exceeds 100 μm

<ITO adhesion evaluation>
The protective film of the two-layer transfer film is peeled off, and a roll temperature of 100 to 150 ° C. is applied by a hot roll laminator (manufactured by Taisei Laminator Co., Ltd., VA-400III) on a substrate on which ITO is previously formed on the front surface of PET. After laminating under conditions of an air pressure of 0.4 MPa and a laminating speed of 1.0 m / min, a 21-step tablet manufactured by Stöffer found in the above-described image formation evaluation was exposed with an exposure amount of 5 steps.

After peeling off the PET film on the support, a 1% by mass Na ₂ CO ₃ aqueous solution at 30 ° C. with a developing cone pressure of 0.15 MPa and a minimum using a full cone type nozzle using a development device manufactured by Fuji Kiko Co., Ltd. Spray and develop for twice the development time, then expose with a 375 mJ / cm ² exposure with a scattered light exposure machine, followed by hot air circulation oven at 145 ° C. for 30 minutes It was cured.

The adhesion evaluation was performed according to JIS K5600-5-6 (adhesion-crosscut method), and was performed according to the following criteria.
○: 4B or more (peeling less than 5%)
X: 3B or less (peeling 5% or more)

3. Evaluation Results Table 1 shows the refractive indexes of the single-layer transfer films obtained in Examples 1 to 8 and Comparative Example 1.
The evaluation results of the two-layer transfer films obtained in Examples 1 to 8 and Comparative Example 1 are shown in Table 1.
From the results shown in Table 1, it can be seen that Examples 1 to 8 have a high refractive index, an image forming property, and an excellent adhesion with ITO by adopting the configuration of the present invention. On the other hand, in Comparative Example 1, generally known zirconia fine particles are used. However, when the amount of zirconia fine particles added is increased in order to achieve a high refractive index, adhesion with ITO is significantly impaired. You can see that

Claims (12)

(A) a resin having an acidic functional group;
(B) a compound having an ethylenically unsaturated double bond;
(C) a photopolymerization initiator; and (D) a heteropolyacid;
A negative photosensitive resin composition comprising: (D) a negative photosensitive resin composition in which the poly atom in the heteropolyacid is tungsten and / or molybdenum.   The negative photosensitive resin composition of Claim 1 whose acidic functional group of the resin which has the said (A) acidic functional group is a carboxyl group.   The negative photosensitive resin composition of Claim 1 or 2 whose content of the said (D) heteropoly acid is 40 mass% or more with respect to the total solid of the said negative photosensitive composition.   The content of the resin having the acidic functional group (A) is 15% by mass to 30% by mass with respect to the total solid content of the negative photosensitive composition, and (B) the ethylenically unsaturated double bond. 4. The content of the compound according to claim 3 is 10% by mass to 20% by mass, and the content of the (C) photopolymerization initiator is 0.1% by mass to 5.0% by mass. Negative photosensitive resin composition.   The negative photosensitive resin composition of any one of Claims 1-4 which is an object for protection of wiring.   The negative photosensitive resin composition of Claim 5 whose said wiring is a transparent electrode.   The negative photosensitive resin composition of Claim 5 or 6 in which the said wiring is formed on the flexible base material.   The transfer material by which the at least 1 layer which consists of a negative photosensitive resin composition of any one of Claims 1-4 was formed on the support film.   A pattern forming method comprising a step of laminating the transfer material according to claim 8 on a base material, exposing and developing to form a pattern.   The pattern formation method of Claim 9 which further includes the process of heating the said pattern. Laminating the transfer material according to claim 8 on a substrate, exposing and developing to form a pattern;
The pattern with heating, obtaining a heat treatment pattern; and further by exposing the heat treatment pattern at an exposure amount of 200 mJ ^/ cm 2 to 500 mJ / cm ^2, and / or is heat treatment A step of further heating the pattern at a temperature of 100 ° C. to 300 ° C. to obtain a cured product;
A cured product production method comprising: A method for producing a touch panel display device by mounting a cured product obtained by the method for producing a cured product according to claim 11 .