JP6136827B2 - Radiation-sensitive resin composition, photosensitive dry film, method for laminating radiation-sensitive resin layer, protective film and touch panel - Google Patents

Description

  The present invention relates to a radiation-sensitive resin composition, a photosensitive dry film, a method for laminating a radiation-sensitive resin layer, a protective film, and a touch panel.

  In recent years, in electronic devices such as PDAs (Personal Digital Assistants), notebook PCs, OA devices, and car navigation systems, touch panels are actively used as input devices for these displays.

  The touch panel touches (presses) the surface with an operator's finger, pen, or the like, and outputs data related to the touch operation to various processing devices, thereby enabling operation of the electronic device. The touch panel is an input device that replaces the keyboard, and enables easy input of information in an interactive manner in the electronic device described above.

  The touch panel includes a resistance film method, a capacitance method, an infrared method, an ultrasonic method, an electromagnetic inductive coupling method, and the like depending on an operation principle.

  In such a touch panel, for example, a plurality of first detection electrodes extending in a predetermined direction and a second detection electrode extending in a direction crossing the plurality of first detection electrodes, such as a capacitance method, are combined to form a transparent substrate such as glass. There is a structure to be placed on top. These detection electrodes are routed to the end of the transparent substrate by wirings electrically connected to each. At the other end of the wiring connected to the detection electrode, for example, a terminal for connecting the touch panel is formed.

  In the capacitance method, for example, as disclosed in Patent Document 1, a structure in which the first detection electrode and the second detection electrode are arranged in the same layer on one surface of the transparent substrate is known. It has been.

  In the touch panel described in Patent Document 1, each of the first detection electrode and the second detection electrode has a rhombus-shaped electrode pad having a large area and a connecting portion having a narrow shape narrower than the electrode pad, which connects between the electrode pads. It consists of. The first detection electrode and the second detection electrode intersect with each other at each connection portion, and a light transmissive interlayer insulating film is disposed at the intersection. Therefore, the touch panel of Patent Document 2 is configured such that the first detection electrode and the second detection electrode are overlapped with each other through the interlayer insulating film at each connection portion to ensure insulation. Then, the first detection electrode and the second detection electrode are routed to the end of the transparent substrate by wirings electrically connected to each. A terminal for connecting a touch panel is formed at the other end of the wiring connected to the detection electrode.

  As described above, a touch panel having a structure having a detection electrode and a wiring for routing the detection electrode to the end of the substrate on an insulating substrate further covers and protects the detection electrode and the wiring. A protective film can be provided (see, for example, Patent Document 2). Such a protective film can be, for example, an organic film made of an organic material. In that case, for the formation of the protective film, it is possible to use a coating method using a liquid resin composition or the like, and patterning may be performed so as to be suitable for the arrangement structure of the detection electrodes of the touch panel. Is possible. Such a protective film can improve reliability such as durability of the touch panel.

JP 2008-310551 A Japanese Patent No. 5212571

  The touch panel having the above-described structure has a detection electrode and a wiring electrically connected to the detection electrode and routed to the end of the substrate on the insulating substrate. The wiring connected to is not directly used for detecting a touch operation with an operator's finger or the like. That is, in the touch panel, the formation area of the wiring connected to each detection electrode is an area not used for the touch operation and its detection.

  Therefore, in the touch panel, the wiring formation region is preferably small and narrow. By narrowing the wiring formation area in this way, the touch panel can be provided with a large operation area where the operator's finger or the like touches to perform a touch operation, and operability can be improved.

  In the touch panel, in order to narrow the wiring formation region, it is preferable to form each wiring electrically connected to the detection electrode. For this purpose, it is required to form the wiring using a low-resistance material. In the touch panel, the wiring connected to the detection electrode is, for example, a metal wiring made of a metal film such as molybdenum (Mo) and aluminum (Al) and having a laminated structure of Mo / Al / Mo. Can do. By having such a constituent material and structure, it is possible to reduce the resistance of the wiring connected to the detection electrode.

  However, when a low-resistance metal wiring is used, there is a problem that the adhesion between them is low when trying to combine with a protective film made of the above-described organic material that can be easily formed and is effective for high reliability. Such low adhesion between the metal wiring and the protective film causes a decrease in the reliability of the touch panel.

  Therefore, in order to improve the metal wiring adhesion, the protective film forming material can contain a component for improving the adhesion. For example, phosphate ester-modified polyfunctional acrylate can be used, and when it is used as a component for forming a protective film, the adhesion between the protective film and the metal wiring can be improved.

  However, as a result of the study, it was found that a protective film using a phosphate ester-modified polyfunctional acrylate as a forming material induces deterioration such as corrosion of metal wiring. This is considered to be because the phosphate ester-modified polyfunctional acrylate increases the moisture permeability of the protective film. As a result, the touch panel is reduced in reliability by using a protective film covering the metal wiring.

  Therefore, in the touch panel, there is a demand for a technique for reducing the resistance of the wiring and realizing high reliability of the touch panel. More specifically, it can be easily formed and patterned from an organic material, has excellent adhesion to metal wiring, and further has a protective film that suppresses the promotion of deterioration such as corrosion of the metal wiring and its formation. Technology is required.

  The present invention has been made in view of the above problems. That is, the objective of this invention is providing the radiation sensitive resin composition which forms the protective film which was excellent in adhesiveness with a metal and suppressed the deterioration acceleration.

  Moreover, the objective of this invention is providing the photosensitive dry film which forms the protective film which was excellent in the adhesiveness with a metal, and suppressed the deterioration acceleration.

  Moreover, the objective of this invention is providing the lamination method of the radiation sensitive resin layer for laminating | stacking the radiation sensitive resin layer which was excellent in adhesiveness with a metal and suppressed the deterioration promotion on a sample.

  Moreover, the objective of this invention is providing the protective film which was excellent in adhesiveness with the metal wiring of a touch panel, and suppressed the deterioration acceleration.

  Furthermore, the objective of this invention is providing the touch panel which has the protective film which was excellent in adhesiveness with metal wiring, and suppressed the deterioration acceleration.

  The first aspect of the present invention includes (A) a binder polymer, (B) a photopolymerization initiator, (C) a compound represented by the following formula (1), and (D) a compound represented by the following formula (2). The present invention relates to a radiation-sensitive resin composition.

(In the formula (1), X represents an oxygen atom or a sulfur atom, R ¹ and R ² each independently represents a single bond or a divalent to tetravalent organic group, and R ³ and ⁴ each independently represent, Any of an unsaturated heterocyclic group, an alkyl group having 11 to 20 carbon atoms, an oxiranyl group, an oxetanyl group, a vinyl group, a (meth) acryloyloxy group, a hydroxyl group, a carboxyl group, an alkoxysilyl group, a mercapto group, and a sulfo group N and m each independently represent an integer of 1 to 3.)

(In Formula (2), R ¹¹ and R ¹² represent a hydrogen atom or a methyl group. J represents an integer of 1 to 5, and k represents an integer of 1 to 2.)

In the first aspect of the present invention, the component (C) is preferably a compound represented by the following formula (3).
(In Formula (3), X represents an oxygen atom or a sulfur atom, R ¹ and R ² each independently represent a single bond or a divalent to tetravalent organic group, and R ⁵ and R ⁶ each independently A hydrogen atom or a methyl group, n and m each independently represent an integer of 1 to 3)

  In the first aspect of the present invention, it is preferable that (E) an unsaturated compound having a urethane bond is further contained.

  In the first embodiment of the present invention, (F) an oxide containing at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, indium, tin, antimony, strontium, barium, cerium and hafnium. It is preferable that the inorganic oxide particle which is a thing is included.

  The 2nd aspect of this invention is related with the photosensitive dry film formed from the radiation sensitive resin composition of the 1st aspect of this invention.

  The 3rd aspect of this invention is a radiation sensitive resin layer formed in the film thickness of 3 micrometers-30 micrometers on the support film using the support film and the radiation sensitive resin composition of the 1st aspect of this invention. And a protective dry film disposed on the radiation-sensitive resin layer.

In a third aspect of the present invention, the radiation-sensitive resin layer is cured by exposure, it is preferable that the water permeability after exposure are 1000g ^{/ m} 2 · 24 hours ~2000g ^{/ m} 2 · 24 hours.

  In the third aspect of the present invention, the support film is preferably polyethylene terephthalate.

A fourth aspect of the present invention is a method for laminating a radiation sensitive resin layer using the photosensitive dry film of the third aspect of the present invention and laminating a radiation sensitive resin layer on a sample,
The present invention relates to a method of laminating a radiation-sensitive resin layer, wherein the radiation-sensitive resin layer is laminated so that the radiation-sensitive resin layer is in close contact with a sample while removing the protective film.

A fifth aspect of the present invention is a protective film for protecting the metal wiring of a touch panel having metal wiring,
A protective film formed by laminating a radiation-sensitive resin layer on a metal wiring and exposing the radiation-sensitive resin layer by the method of laminating a radiation-sensitive resin layer according to the fourth aspect of the present invention. About.

  A 6th aspect of this invention is related with the touchscreen characterized by having a metal wiring and the protective film of the 5th aspect of this invention.

  According to the 1st aspect of this invention, the radiation sensitive resin composition which is excellent in adhesiveness with a metal and forms the protective film which suppressed the deterioration promotion can be provided.

  According to the 2nd aspect of this invention, the photosensitive dry film which forms the protective film which was excellent in the adhesiveness with a metal and suppressed the deterioration promotion can be provided.

  According to the 3rd aspect of this invention, the photosensitive dry film which forms the protective film which was excellent in the adhesiveness with a metal and suppressed the deterioration promotion can be provided.

  According to the fourth aspect of the present invention, there is provided a method for laminating a radiation-sensitive resin layer for laminating a radiation-sensitive resin layer having excellent adhesion to metal and suppressing its deterioration promotion on a sample. Can do.

  According to the fifth aspect of the present invention, it is possible to provide a protective film that is excellent in adhesion to the metal wiring of the touch panel and suppresses the deterioration promotion.

  According to the sixth aspect of the present invention, it is possible to provide a touch panel having a protective film that has excellent adhesion to metal wiring and suppresses the deterioration promotion.

It is typical sectional drawing which shows the photosensitive dry film of 2nd Embodiment of this invention. It is a top view which shows the touchscreen which is 3rd Embodiment of this invention. FIG. 3 is a cross-sectional view taken along line B-B ′ of FIG. 2.

  As a result of intensive studies, the present inventor, for example, in the case where a protective film that covers and protects a metal material such as a metal wiring of a touch panel is an organic film made of an organic material, the formation material is modified with a phosphate ester-modified polymer. It was confirmed that the adhesion between the metal material and the protective film can be improved by using the functional acrylate. On the other hand, it has been found that a protective film using a phosphate ester-modified polyfunctional acrylate increases moisture permeability and induces deterioration such as corrosion of a metal material. Therefore, for example, when a protective film using a phosphate ester-modified polyfunctional acrylate is applied to a touch panel having a metal wiring having a laminated structure of Mo / Al / Mo, deterioration such as corrosion of the wiring Is triggered.

  Therefore, the present inventor conducted further studies and maintained excellent adhesion between the obtained protective film and the metal material by using a specific component in the formation of the protective film made of an organic material. It was found that the deterioration of the material such as corrosion can be suppressed. A protective film that is an organic film made of an organic material can be formed using a radiation-sensitive resin composition that is a radiation-sensitive resin composition. Therefore, by including a phosphate ester-modified polyfunctional acrylate-based component and a specific component as a component of the radiation-sensitive resin composition, improved adhesion to metal materials in the formed organic film It is possible to suppress the deterioration of the metal material.

  Therefore, a cured film obtained by using the radiation-sensitive resin composition of the present invention obtained as a result of the study and curing it has excellent adhesion to a metal material, while the acceleration of deterioration such as corrosion is reduced. It can be used as a protective film. That is, by using the radiation sensitive resin composition of the present invention, for example, a protective film suitable for a touch panel having a metal wiring having a laminated structure of Mo / Al / Mo can be provided. . The protective film formed using the radiation-sensitive resin composition of the present invention has excellent adhesion to metal wiring, and prevents deterioration such as corrosion, thereby realizing high reliability of the touch panel. can do.

Hereinafter, embodiments of the present invention such as a radiation sensitive resin composition and a touch panel will be described with reference to the drawings as appropriate.
In the present invention, “radiation” irradiated upon exposure includes visible light, ultraviolet light, far ultraviolet light, X-rays, charged particle beams, and the like.

Embodiment 1 FIG.
<Radiation sensitive resin composition>
The radiation-sensitive resin composition according to the first embodiment of the present invention is a protective film having excellent adhesion to a metal material, and can prevent the deterioration of corrosion and the like of the metal material to be protected from being accelerated. It is a radiation-sensitive resin composition suitable for forming. And the touch panel of embodiment of this invention mentioned later can have the metal wiring etc. which were comprised with the laminated structure used as Mo / Al / Mo, for example. Therefore, the radiation sensitive resin composition of 1st Embodiment of this invention can provide the protective film which can be used suitably for the touchscreen of embodiment of this invention.

  The radiation-sensitive resin composition according to the second embodiment of the present invention includes (A) a binder polymer (sometimes simply referred to as (A) component), (B) a photopolymerization initiator (only (B). (C) a compound represented by the following formula (1) (sometimes simply referred to as the component (C) or (C) compound), and (D) the following formula (2). ) (Which may be simply referred to as component (D) or (D) compound).

(In the formula (1), X represents an oxygen atom or a sulfur atom, R ¹ and R ² each independently represents a single bond or a divalent to tetravalent organic group, and R ³ and ⁴ each independently represent, Any of an unsaturated heterocyclic group, an alkyl group having 11 to 20 carbon atoms, an oxiranyl group, an oxetanyl group, a vinyl group, a (meth) acryloyloxy group, a hydroxyl group, a carboxyl group, an alkoxysilyl group, a mercapto group, and a sulfo group N and m each independently represent an integer of 1 to 3.)

(In Formula (2), R ¹¹ and R ¹² represent a hydrogen atom or a methyl group. J represents an integer of 1 to 5, and k represents an integer of 1 to 2.)

  Hereinafter, each component contained in the radiation sensitive resin composition of this embodiment is explained in full detail.

[(A) Binder polymer]
The binder polymer (A) contained in the radiation-sensitive resin composition of the embodiment of the present invention is at least one selected from the group consisting of (a1) an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride (hereinafter, It is a copolymer of “compound (a1)”) and (a2) another unsaturated compound (hereinafter referred to as “compound (a2)”).

  In the present embodiment, (A) the binder polymer is referred to as [A1] compound (a1) and an unsaturated compound containing one or more hydroxyl groups in one molecule (hereinafter referred to as “compound (a2-1)”). ) (Hereinafter referred to as “copolymer [α]”) and a polymer obtained by reacting an unsaturated isocyanate compound (hereinafter referred to as “copolymer [A1]”), and [ A2] A copolymer of the compound (a1) and an unsaturated compound having an oxiranyl group or an oxetanyl group (hereinafter referred to as “compound (a2-2)”) (hereinafter referred to as “copolymer [A2]”). At least one selected from the group consisting of is preferred.

As the compound (a1), for example,
Monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl hexahydrophthalic acid, 2-methacryloyloxyethyl hexahydrophthalic acid;
Dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid;
The acid anhydride of the said dicarboxylic acid etc. can be mentioned.

  Of these compounds (a1), acrylic acid, methacrylic acid, maleic anhydride and the like are preferable from the viewpoints of copolymerization reactivity, solubility of the resulting polymer and copolymer in an alkaline developer, and easy availability. .

  In the copolymer [α] and the copolymer [A2], the compound (a1) can be used alone or in admixture of two or more.

  In the copolymer [α] and the copolymer [A2], the content of the repeating unit derived from the compound (a1) is preferably 5% by weight to 50% by weight, more preferably 10% by weight to 40% by weight, More preferably, it is 15 to 30% by weight. If the content of the repeating unit derived from the compound (a1) is less than 5% by weight, the solubility of the resulting polymer in an alkaline developer tends to be reduced, whereas if it exceeds 50% by weight, There is a possibility that the solubility in an alkali developer becomes too large.

  In the case where the compound (a1) has a carboxyl group, the carboxyl group may be regenerated by protecting it and then subjecting it to polymerization, followed by deprotection. Here, the protecting group for protecting the carboxyl group is not particularly limited, and a known protecting group for the carboxyl group can be used. For example, a trialkylsilyl group, 1-alkoxyalkyl group, cyclic 1-alkoxyalkyl group and the like can be mentioned. More specifically, for example, trimethylsilyl group, dimethylbutylsilyl group, 1-ethoxyethyl group, 1-propoxyethyl group, tetrahydrofuranyl group, tetrahydropyranyl group, triphenylmethyl group and the like can be mentioned.

Examples of the compound (a2-1) in the copolymer [α] include (meth) acrylic acid 2-hydroxyethyl ester, (meth) acrylic acid 3-hydroxypropyl ester, (meth) acrylic acid 4-hydroxybutyl ester. , (Meth) acrylic acid 5-hydroxypentyl ester, (meth) acrylic acid 6-hydroxyhexyl ester, (meth) acrylic acid 7-hydroxyheptyl ester, (meth) acrylic acid 8-hydroxyoctyl ester, (meth) acrylic acid (Meth) acrylic acid hydroxyalkyl esters such as 9-hydroxynonyl ester, (meth) acrylic acid 10-hydroxydecyl ester, (meth) acrylic acid 11-hydroxyundecyl ester, (meth) acrylic acid 12-hydroxydodecyl ester;
(Meth) acrylic acid 4-hydroxy-cyclohexyl ester, (meth) acrylic acid 4-hydroxymethyl-cyclohexyl methyl ester, (meth) acrylic acid 4-hydroxyethyl-cyclohexyl ethyl ester, (meth) acrylic acid 3-hydroxy-bicyclo [2.2.1] hept-5-en-2-yl ester, (meth) acrylic acid 3-hydroxymethyl-bicyclo [2.2.1] hept-5-en-2-ylmethyl ester, (meth ) Acrylic acid 3-hydroxyethyl-bicyclo [2.2.1] hept-5-en-2-ylethyl ester, (meth) acrylic acid 8-hydroxy-bicyclo [2.2.1] hept-5-ene 2-yl ester, (meth) acrylic acid 2-hydroxy-octahydro-4,7-methano-indene-5 Yl ester, (meth) acrylic acid 2-hydroxymethyl-octahydro-4,7-methano-indene-5-ylmethyl ester, (meth) acrylic acid 2-hydroxyethyl-octahydro-4,7-methano-indene-5 -Ylethyl ester, (meth) acrylic acid 3-hydroxy-adamantan-1-yl ester, (meth) acrylic acid 3-hydroxymethyl-adamantan-1-ylmethyl ester, (meth) acrylic acid 3-hydroxyethyl-adamantane (Meth) acrylic acid hydroxyalkyl ester having an alicyclic structure such as -1-ylethyl ester;

(Meth) acrylic acid 1,2-dihydroxyethyl ester, (meth) acrylic acid 2,3-dihydroxypropyl ester, (meth) acrylic acid 1,3-dihydroxypropyl ester, (meth) acrylic acid 3,4-dihydroxybutyl ester Esters, (meth) acrylic acid dihydroxyalkyl esters such as 3- [3- (2,3-dihydroxypropoxy) -2-hydroxypropoxy] -2-hydroxypropyl ester;
Acrylic acid 2- (6-hydroxyhexanoyloxy) ethyl ester, acrylic acid 3- (6-hydroxyhexanoyloxy) propyl ester, acrylic acid 4- (6-hydroxyhexanoyloxy) butyl ester, acrylic acid 5- ( 6-hydroxyhexanoyloxy) pentyl ester, acrylic acid (6-hydroxyhexanoyloxy) alkyl ester such as acrylic acid 6- (6-hydroxyhexanoyloxy) hexyl ester;
Methacrylic acid 2- (6-hydroxyhexanoyloxy) ethyl ester, methacrylic acid 3- (6-hydroxyhexanoyloxy) propyl ester, methacrylic acid 4- (6-hydroxyhexanoyloxy) butyl ester, methacrylic acid 5- ( Other compounds (a2-1) such as 6-hydroxyethylhexanoyloxy) pentyl ester, methacrylic acid (6-hydroxyhexanoyloxy) alkyl ester such as methacrylic acid 6- (6-hydroxyhexanoyloxy) hexyl ester (Hereinafter referred to as “other compound (a2-1)”).

  Of these compounds (a2-1), from the viewpoint of copolymerization reactivity and reactivity with isocyanate compounds, acrylic acid 2-hydroxyethyl ester, acrylic acid 3-hydroxypropyl ester, acrylic acid 4-hydroxybutyl ester, Methacrylic acid 2-hydroxyethyl ester, Methacrylic acid 3-hydroxypropyl ester, Methacrylic acid 4-hydroxybutyl ester, Acrylic acid 4-hydroxymethyl-cyclohexyl methyl ester, Methacrylic acid 4-hydroxymethyl-cyclohexyl methyl ester, Acrylic acid 2, 3-dihydroxypropyl ester, methacrylic acid 2,3-dihydroxypropyl ester, other compounds (a2-1) and the like are preferable.

  Among the compounds (a2-1), the other compound (a2-1) is particularly preferable from the viewpoint of improving developability and improving the strength of the protective film obtained. Among other compounds (a2-1), acrylic acid 2- (6-hydroxyhexanoyloxy) ethyl ester and methacrylic acid 2- (6-hydroxyhexanoyloxy) ethyl ester are preferable, and methacrylic acid 2- (6 As a commercial product of a mixture of -hydroxyhexanoyloxy) ethyl ester and methacrylic acid 2-hydroxyethyl ester, PLACEL (registered trademark) FM1D, FM2D (manufactured by Daicel Chemical Industries, Ltd.) and the like can be given as trade names. it can.

  In the copolymer [α], the compound (a2-1) can be used alone or in admixture of two or more.

  In the copolymer [α], the content of the repeating unit derived from the compound (a2-1) is preferably 1% by weight to 50% by weight, more preferably 3% by weight to 40% by weight, and still more preferably 5% by weight. % To 30% by weight. If the content of the repeating unit derived from the compound (a2-1) is less than 1% by weight, the introduction rate of the unsaturated isocyanate compound into the polymer tends to be lowered, and the sensitivity tends to be lowered, while 50% by weight is reduced. When it exceeds, there exists a tendency for the storage stability of the polymer obtained by reaction with an unsaturated isocyanate compound to fall.

Examples of the compound (a2-2) in the copolymer [A2] include glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, and (meth) acrylic. (Meth) acrylic such as 3,4-epoxybutyl acid, 6,7-epoxyheptyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate Acid epoxy (cyclo) alkyl esters;
α-ethyl acrylate glycidyl, α-n-propyl acrylate glycidyl, α-n-butyl acrylate glycidyl, α-ethyl acrylate 6,7-epoxyheptyl, α-ethyl acrylate 3,4-epoxycyclohexyl, etc. Other α-alkyl acrylic acid epoxy (cyclo) alkyl esters;
glycidyl ethers such as o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether;
3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2-methyloxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-pentafluoroethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 3- (methacryloyloxymethyl) -2,2-difluorooxetane, 3- (methacryloyloxymethyl) ) -2,2,4-trifluorooxetane, 3- (methacryloyloxymethyl) -2,2,4,4-tetrafluorooxetane, 3- (methacryloyloxyethyl) oxetane, 3- (methacryloyloxyethyl) -3 -Ethyloxy Tan, 2-ethyl-3- (methacryloyloxyethyl) oxetane, 3- (methacryloyloxyethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxyethyl) -2-pentafluoroethyloxetane, 3- (methacryloyloxy) Ethyl) -2-phenyloxetane, 2,2-difluoro-3- (methacryloyloxyethyl) oxetane, 3- (methacryloyloxyethyl) -2,2,4-trifluorooxetane, 3- (methacryloyloxyethyl) -2 Methacrylic acid esters such as 1,2,4,4-tetrafluorooxetane;

3- (acryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) -3-ethyloxetane, 3- (acryloyloxymethyl) -2-methyloxetane, 3- (acryloyloxymethyl) -2-trifluoromethyloxetane, 3- (acryloyloxymethyl) -2-pentafluoroethyloxetane, 3- (acryloyloxymethyl) -2-phenyloxetane, 3- (acryloyloxymethyl) -2,2-difluorooxetane, 3- (acryloyloxymethyl) ) -2,2,4-trifluorooxetane, 3- (acryloyloxymethyl) -2,2,4,4-tetrafluorooxetane, 3- (acryloyloxyethyl) oxetane, 3- (acryloyloxyethyl) -3 -Ethyloxetane, 2-ethyl-3 (Acryloyloxyethyl) oxetane, 3- (acryloyloxyethyl) -2-trifluoromethyloxetane, 3- (acryloyloxyethyl) -2-pentafluoroethyloxetane, 3- (acryloyloxyethyl) -2-phenyloxetane, 2,2-difluoro-3- (acryloyloxyethyl) oxetane, 3- (acryloyloxyethyl) -2,2,4-trifluorooxetane, 3- (acryloyloxyethyl) -2,2,4,4-tetra Acrylic esters such as fluorooxetane are mentioned.

  Among these, glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3-methyl-3-methacryloyloxymethyloxetane, 3-ethyl- 3-Methacryloyloxymethyloxetane and the like are preferable from the viewpoint of polymerizability.

  In the copolymer [A2], the compound (a2-2) can be used alone or in admixture of two or more.

  In the copolymer [A2], the content of the repeating unit derived from the compound (a2-2) is preferably 0.5% to 70% by weight, more preferably 1% to 60% by weight, and still more preferably. 3% to 50% by weight. When the content of the repeating unit derived from the compound (a2-2) is less than 0.5% by weight, the heat resistance of the resulting copolymer tends to be reduced. On the other hand, when the content exceeds 70% by weight, Storage stability tends to decrease.

In the copolymer [α] and the copolymer [A2], the compound (a2) other than the compound (a2-1) and the compound (a2-2) “hereinafter referred to as“ compound (a2-3) ”. Can be used as a component of the copolymer. Specific examples thereof include alkyl acrylates such as methyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, sec-butyl acrylate, and t-butyl acrylate;
Alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate;
Cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.02,6] decan-8-yl acrylate, 2- (tricyclo [5.2.1.02,6] decane-acrylate Acrylic acid alicyclic esters such as 8-yloxy) ethyl, isobornyl acrylate;
Cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.02,6] decan-8-yl methacrylate, 2- (tricyclo [5.2.1.02,6] decane methacrylate) Methacrylic acid alicyclic esters such as 8-yloxy) ethyl, isobornyl methacrylate;
Aryl esters or aralkyl esters of acrylic acid such as phenyl acrylate and benzyl acrylate;
Aryl esters or aralkyl esters of methacrylic acid such as phenyl methacrylate and benzyl methacrylate;
Unsaturated dicarboxylic acid dialkyl esters such as diethyl maleate, diethyl fumarate, diethyl itaconate;
Acrylic acid ester having an oxygen-containing hetero 5-membered ring or an oxygen-containing hetero 6-membered ring such as tetrahydrofuran-2-yl acrylate, tetrahydropyran-2-yl acrylate, 2-methyltetrahydropyran-2-yl acrylate;
Methacrylic acid ester having an oxygen-containing hetero 5-membered ring or an oxygen-containing hetero 6-membered ring such as tetrahydrofuran-2-yl methacrylate, tetrahydropyran-2-yl methacrylate, 2-methyltetrahydropyran-2-yl methacrylate;
Vinyl aromatic compounds such as styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene;
In addition to conjugated diene compounds such as 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene,
Examples include acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, vinyl chloride, vinylidene chloride, and vinyl acetate.

  Among these, from the viewpoint of copolymerization reactivity, n-butyl methacrylate, 2-methylglycidyl methacrylate, benzyl methacrylate, tricyclo [5.2.1.02,6] decan-8-yl methacrylate, Styrene, p-methoxystyrene, tetrahydrofuran-2-yl methacrylate, 1,3-butadiene and the like are preferable.

  In the copolymer [α] and the copolymer [A2], the compound (a2-3) can be used alone or in admixture of two or more.

  In the copolymer [α] and the copolymer [A2], the content of the repeating unit derived from the compound (a2-3) is preferably 10% by weight to 70% by weight, more preferably 20% by weight to 50% by weight. %, More preferably 30% to 50% by weight. When the content of the repeating unit of the compound (a2-3) is less than 10% by weight, the molecular weight of the copolymer tends to decrease. On the other hand, when the content exceeds 70% by weight, the compound (a1) and the compound (a2-1) And the effect which a compound (a2-2) ingredient shows falls.

  The copolymer [α] and the copolymer [A2] can be produced by polymerization in a suitable solvent in the presence of a radical polymerization initiator.

As the solvent used for the polymerization, for example,
Alcohols such as methanol, ethanol, n-propanol, i-propanol;
Ethers such as tetrahydrofuran and dioxane;
Ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether;
Ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether acetate, ethylene glycol mono-n-butyl ether acetate;
Ethylene glycol monoalkyl ether propionates such as ethylene glycol monomethyl ether propionate, ethylene glycol monoethyl ether propionate, ethylene glycol mono-n-propyl ether propionate, ethylene glycol mono-n-butyl ether propionate;
Diethylene glycol alkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether;
Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether;
Dipropylene glycol alkyl ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol methyl ethyl ether;

Propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, propylene glycol mono-n-butyl ether acetate;
Propylene glycol monoalkyl ether propionate such as propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, propylene glycol mono-n-propyl ether propionate, propylene glycol mono-n-butyl ether propionate;
Aromatic hydrocarbons such as toluene and xylene;
Ketones such as methyl ethyl ketone, 2-pentanone, 3-pentanone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone;
Methyl 2-methoxypropionate, ethyl 2-methoxypropionate, n-propyl 2-methoxypropionate, n-butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-ethoxypropion N-propyl acid, n-butyl 2-ethoxypropionate, methyl 2-n-propoxypropionate, ethyl 2-n-propoxypropionate, n-propyl 2-n-propoxypropionate, 2-n-propoxypropionic acid n-butyl, methyl 2-n-butoxypropionate, ethyl 2-n-butoxypropionate, n-propyl 2-n-butoxypropionate, n-butyl 2-n-butoxypropionate, methyl 3-methoxypropionate , Ethyl 3-methoxypropionate, 3-methoxy N-propyl propionate, n-butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, n-propyl 3-ethoxypropionate, n-butyl 3-ethoxypropionate, 3-n -Methyl propoxypropionate, ethyl 3-n-propoxypropionate, n-propyl 3-n-propoxypropionate, n-butyl 3-n-propoxypropionate, methyl 3-n-butoxypropionate, 3-n- Alkyl alkoxypropionates such as ethyl butoxypropionate, n-propyl 3-n-butoxypropionate, n-butyl 3-n-butoxypropionate;

Methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, methyl hydroxyacetate, ethyl hydroxyacetate, n-propyl hydroxyacetate, n-butyl hydroxyacetate, 4-methoxybutyl acetate, 3-methoxybutyl acetate, acetic acid 2 -Methoxybutyl, 3-ethoxybutyl acetate, 3-proxybutyl acetate, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, methyl 2-hydroxy-2-methylpropionate, 2-hydroxy-2-methyl Ethyl propionate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, n-propyl 3-hydroxypropionate, n-butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, Ethoxy methoxyacetate, methoxyacetic acid -Propyl, n-butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, n-propyl ethoxyacetate, n-butyl ethoxyacetate, methyl n-propoxyacetate, ethyl n-propoxyacetate, n-propyloxyacetate n-propyl, n Examples include other esters such as n-butyl propoxyacetate, methyl n-butoxyacetate, ethyl n-butoxyacetate, n-propyl n-butoxyacetate, n-butyl n-butoxyacetate, and the like.

Of these solvents, diethylene glycol alkyl ether, propylene glycol monoalkyl ether acetate, alkyl alkoxypropionate, acetate, and the like are preferable.
The said solvent can be used individually or in mixture of 2 or more types.

  The radical polymerization initiator is not particularly limited. For example, 2,2′-azobisisobutyronitrile, 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2 '-Azobis- (4-methoxy-2,4-dimethylvaleronitrile), 4,4'-azobis (4-cyanovaleric acid), dimethyl-2,2'-azobis (2-methylpropionate), 2, Azo compounds such as 2′-azobis (4-methoxy-2,4-dimethylvaleronitrile); organics such as benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, 1,1-bis (t-butylperoxy) cyclohexane Peroxide; hydrogen peroxide and the like.

When a peroxide is used as a radical polymerization initiator, it may be used in combination with a reducing agent to form a redox initiator.
These radical polymerization initiators can be used alone or in admixture of two or more.

  The copolymer [α] and the copolymer [A2] thus obtained can be used in the production of the copolymer [A1] as they are in solution, or once separated from the solution, the copolymer [A1] You may use for manufacture of this.

  The weight average molecular weight (hereinafter referred to as “Mw”) in terms of polystyrene by gel permeation chromatography (GPC) of the copolymer [α] and the copolymer [A2] is preferably 2000 to 100,000, more preferably 5000 to 50000. It is. If the Mw is less than 2000, the alkali developability and the remaining film ratio of the resulting film may be reduced, and the pattern shape, heat resistance, etc. may be impaired. On the other hand, if it exceeds 100,000, the resolution will be reduced. Or the pattern shape may be damaged.

The copolymer [A1] in this embodiment is obtained by reacting the copolymer [α] with an unsaturated isocyanate compound.
Examples of unsaturated isocyanate compounds include:
2-acryloyloxyethyl isocyanate, 3-acryloyloxypropyl isocyanate, 4-acryloyloxybutyl isocyanate, 6-acryloyloxyhexyl isocyanate, 8-acryloyloxyoctyl isocyanate, 10-acryloyloxydecyl isocyanate,
2- (2-isocyanatoethoxy) ethyl acrylate,
2- [2- (2-isocyanatoethoxy) ethoxy] ethyl acrylate,
2- {2- [2- (2-isocyanatoethoxy) ethoxy] ethoxy} ethyl acrylate, 2- (2-isocyanatopropoxy) ethyl acrylate,
Acrylic acid derivatives such as acrylic such as 2- [2- (2-isocyanatopropoxy) propoxy] ethyl acrylate;
2-methacryloyloxyethyl isocyanate, 3-methacryloyloxypropyl isocyanate, 4-methacryloyloxybutyl isocyanate, 6-methacryloyloxyhexyl isocyanate, 8-methacryloyloxyoctyl isocyanate, 10-methacryloyloxydecyl isocyanate 2- (2-isocyanatoethoxy) )ethyl,
2- [2- (2-isocyanatoethoxy) ethoxy] ethyl methacrylate,
2- {2- [2- (2-isocyanatoethoxy) ethoxy] ethoxy} ethyl methacrylate,
2- (2-isocyanatopropoxy) ethyl methacrylate,
Mention may be made of methacrylic acid derivatives such as 2- [2- (2-isocyanatopropoxy) propoxy] ethyl methacrylate.

  Moreover, as a commercial item of 2-acryloyloxyethyl isocyanate, it is a trade name, Karenz AOI (made by Showa Denko KK), and as a commercial item of 2-methacryloyloxyethyl isocyanate, it is a brand name, Karenz MOI (registered trademark). ) (Manufactured by Showa Denko Co., Ltd.) and commercial products of 2- (2-isocyanatoethoxy) ethyl methacrylate include Karenz MOI (registered trademark) -EG (manufactured by Showa Denko Co., Ltd.) under the trade name. Can do.

Among these unsaturated isocyanate compounds, 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, 4-methacryloyloxybutyl isocyanate, methacrylic acid 2- (2) from the viewpoint of reactivity with the copolymer [α]. -Isocyanatoethoxy) ethyl and the like are preferred.
In the copolymer [A1], the unsaturated isocyanate compound can be used alone or in admixture of two or more.

  In the present embodiment, the reaction between the copolymer [α] and the unsaturated isocyanate compound includes, for example, a copolymer containing a catalyst such as di-n-butyltin (IV) dilaurate and a polymerization inhibitor such as p-methoxyphenol. It can be carried out by adding an unsaturated isocyanate compound to the polymer [α] solution while stirring at room temperature or under heating.

  The amount of the unsaturated isocyanate compound used in the production of the copolymer [A1] is preferably 0.1 mol relative to 1 equivalent of the hydroxyl group derived from the compound (a2-1) in the copolymer [α]. % To 95 mol%, more preferably 1.0 mol% to 80 mol%, particularly preferably 5.0 mol% to 75 mol%. When the amount of the unsaturated isocyanate compound used is less than 0.1 mol%, the effect of improving the sensitivity and heat resistance is small. On the other hand, when it exceeds 95 mol%, the unreacted unsaturated isocyanate compound remains and the resulting polymer is obtained. The storage stability of the solution or the radiation sensitive resin composition tends to be lowered.

  (A) As the binder polymer, the copolymer [A1] and the copolymer [A2] can be used alone, respectively, but the storage stability of the resulting radiation-sensitive resin composition and the strength of the protective film In view of further improving the heat resistance, it is preferable to use the copolymer [A1] and the copolymer [A2] in combination.

  In this embodiment, when the copolymer [A1] and the copolymer [A2] are used in combination as the (A) binder polymer, the amount of the copolymer [A2] used is 100 parts by weight of the copolymer [A1]. Is preferably 0.5 to 50 parts by weight, more preferably 1 to 40 parts by weight, still more preferably 3 to 30 parts by weight. When the amount of the copolymer [A2] used is less than 0.5 parts by weight, the effect of improving the strength and heat resistance of the protective film is small, while when it exceeds 50 parts by weight, the storage stability of the radiation-sensitive resin composition is reduced. There is a tendency to decrease.

[(B) Photopolymerization initiator]
Examples of the (B) photopolymerization initiator contained in the radiation-sensitive resin composition of the embodiment of the present invention include an O-acyl oxime compound, an acetophenone compound, a biimidazole compound, a benzoin compound, a benzophenone compound, and an α-diketone. Compounds, polynuclear quinone compounds, xanthone compounds, phosphine compounds, triazine compounds and the like can be mentioned.

  Examples of the O-acyloxime compound include 1- [9-ethyl-6-benzoyl-9. H. -Carbazol-3-yl] -nonane-1,2-nonane-2-oxime-O-benzoate, 1- [9-ethyl-6-benzoyl-9. H. -Carbazol-3-yl] -nonane-1,2-nonane-2-oxime-O-acetate, 1- [9-ethyl-6-benzoyl-9. H. -Carbazol-3-yl] -pentane-1,2-pentane-2-oxime-O-acetate, 1- [9-ethyl-6-benzoyl-9. H. -Carbazol-3-yl] -octane-1-one oxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-acetate, 1- [9-ethyl-6- (1,3,5-trimethylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate, 1- [9-butyl-6- (2-ethylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate, 1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylmethoxybenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-acetate, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-acetate, ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazole-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl } -9. H. -Carbazol-3-yl] -1- (O-acetyloxime) and the like.

  Of these O-acyloxime compounds, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-acetate, 1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylmethoxybenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-acetate, ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxy Benzoyl} -9. H. -Carbazol-3-yl] -1- (O-acetyloxime) is preferred.

  These O-acyloxime compounds can be used alone or in admixture of two or more.

  Examples of the acetophenone compound include an α-hydroxyketone compound and an α-aminoketone compound.

  Examples of the α-hydroxyketone compound include 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1- (4-i-propylphenyl) -2-hydroxy-2-methylpropane-1- ON, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenylketone and the like. Examples of the α-aminoketone compound include 2-methyl -1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- (4-methylbenzyl) ) -2- (dimethylamino) -1- (4-morpholinophenyl) -butan-1-one and the like. Examples of compounds other than these include 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, and the like.

  Among these acetophenone compounds, in particular, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2- (4-methylbenzyl) -2- (dimethylamino) -1- ( 4-morpholinophenyl) -butan-1-one is preferred.

  In the present embodiment, the sensitivity and the strength of the protective film can be further improved by using the acetophenone compound together.

  Examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2'-bis (2-bromophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2-chlorophenyl)- 4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1, 2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2-Bromophenyl) -4,4 ' 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4-dibromophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-bi Examples thereof include imidazole and 2,2′-bis (2,4,6-tribromophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole.

  Among these biimidazole compounds, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2, 4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5 5′-tetraphenyl-1,2′-biimidazole and the like are preferable, and 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′- is particularly preferable. Biimidazole is preferred.

  In the present embodiment, by using a biimidazole compound in combination, it is possible to further improve sensitivity, resolution, and protective film adhesion.

  When a biimidazole compound is used in combination, an aliphatic or aromatic compound having a dialkylamino group (hereinafter referred to as “amino sensitizer”) can be added to sensitize it.

  Examples of the amino sensitizer include N-methyldiethanolamine, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, ethyl p-dimethylaminobenzoate, and p-dimethylaminobenzoate. An acid i-amyl etc. can be mentioned.

Of these amino sensitizers, 4,4′-bis (diethylamino) benzophenone is particularly preferable.
The amino sensitizers can be used alone or in admixture of two or more.

  When a biimidazole compound and an amino sensitizer are used in combination, the addition amount of the amino sensitizer is preferably 1 to 200 parts by weight, more preferably 10 parts by weight to 100 parts by weight of the biimidazole compound. 150 parts by weight. In this case, when the addition amount of the amino sensitizer is less than 1 part by weight, the effect of improving the sensitivity, resolution and adhesion tends to be reduced. On the other hand, when it exceeds 200 parts by weight, the resulting patterning property tends to be impaired. There is.

  Furthermore, when using a biimidazole compound and an amino sensitizer together, a thiol compound can be added as a hydrogen donor compound. The biimidazole compound is sensitized and cleaved by the amino sensitizer to generate an imidazole radical, but as it is, a high polymerization initiating ability is not expressed, and the resulting protective film cannot be patterned successfully, which is an undesirable shape. In many cases. However, by adding a thiol compound to a system in which a biimidazole compound and an amino sensitizer coexist, hydrogen radicals are donated from the thiol compound to the imidazole radical, so that the imidazole radical is converted to neutral imidazole. At the same time, a component having a sulfur radical having a high polymerization initiating ability is generated, whereby the protective film can be patterned as desired.

  Examples of the thiol compound include aromatic compounds such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazole, and 2-mercapto-5-methoxybenzimidazole. Aliphatic monothiols such as 3-mercaptopropionic acid, methyl 3-mercaptopropionate, ethyl 3-mercaptopropionate, octyl 3-mercaptopropionate; 3,6-dioxa-1,8-octanedithiol, pentaerythritol Bifunctional or higher aliphatic thiols such as tetra (mercaptoacetate) and pentaerythritol tetra (3-mercaptopropionate) can be mentioned.

  Of these thiol compounds, 2-mercaptobenzothiazole is particularly preferable.

  The addition amount of the thiol compound is preferably 1 part by weight to 150 parts by weight, more preferably 10 parts by weight to 100 parts by weight with respect to 100 parts by weight of the biimidazole compound. In this case, when the addition amount of the thiol compound is less than 1 part by weight, the effect of improving the patterning property of the protective film tends to be reduced or the film tends to be reduced. There exists a tendency for patterning property to be impaired.

  In the radiation-sensitive resin composition of the present embodiment, the amount of (B) photopolymerization initiator used is 100 parts by weight in total of the component (A), the component (C) described later, and the component (D) described later. The amount is preferably 5 to 30 parts by weight, more preferably 5 to 25 parts by weight. In this case, if the amount of use by weight is less than 5 parts by weight, the residual film ratio at the time of development with a developer comprising an alkaline aqueous solution tends to decrease, whereas if it exceeds 30 parts by weight, the developer in the unexposed part There is a tendency for the solubility to be reduced.

[(C) Compound]
The (C) compound contained in the radiation sensitive resin composition of the embodiment of the present invention is a compound represented by the following formula (1). (C) The compound has a —NH—CO—NH— moiety or —NH—CS—NH— moiety of the formula (1). Since the compound (C) has weak nucleophilicity at these sites, the protective film formed using the radiation-sensitive resin composition of this embodiment induces deterioration such as corrosion of the metal material to be protected. Can be suppressed. And unlike a normal basic compound, even if it uses abundantly, the adhesive force to the metal material of the protective film formed using the radiation sensitive resin composition of this embodiment is not reduced.

In the above formula (1), X represents an oxygen atom or a sulfur atom, R ¹ and R ² each independently represent a single bond or a divalent to tetravalent organic group, and R ³ and R ⁴ each independently , Unsaturated heterocyclic group, alkyl group having 11 to 20 carbon atoms, oxiranyl group, oxetanyl group, vinyl group, (meth) acryloyloxy group, hydroxyl group, carboxyl group, alkoxysilyl group, mercapto group and sulfo group Indicate. n and m each independently represent an integer of 1 to 3.

More specifically, in the above formula (1), preferred examples of R ¹ and R ² include single bond, methylene group, ethylene group, propylene group, butylene group, heptylene group, hexamethylene group, phenylene group,- (C ₂ H ₄ O) _ma C ₂ H ₄ —, — (C ₃ H ₆ O) _ma C ₂ H ₄ — (ma represents an integer of 1 to 5), the following formula (4a), the following formula ( And the group represented by 4b).

  In the above formulas (4a) and (4b), e, f, g and h may be the same as or different from each other, and represent an integer of 0 to 12.

In the above formula (1), R ³ and R ⁴ are each independently an unsaturated heterocyclic group, an alkyl group having 11 to 20 carbon atoms, an oxiranyl group, an oxetanyl group, a vinyl group, a (meth) acryloyloxy group, a hydroxyl group, A carboxyl group, an alkoxysilyl group, a mercapto group, and a sulfo group are shown.

  An unsaturated heterocyclic group is distinguished from an aryl group (aromatic hydrocarbon group) and represents a heterocyclic group having an unsaturated bond. Specifically, 2-furyl group, furfuryl group, 2-thienyl group, 2-thenyl group, 2-thenoyl group, 2-pyrrolyl group, 2-pyridyl group, 2-quinoyl group, carbazole group, imidazole group, benzoic group An imidazole group, an indole group, etc. are shown.

  In said formula (1), n and m show the integer of 1-3 each independently.

  Among the compounds (C), a compound having a polymerizable group at both ends as shown by the following formula (3) is particularly preferable. In addition to the effect of the compound (C) described above, such a compound is capable of further increasing the hardness of the cured film by thermally crosslinking the polymerizable group by heating at the time of post-baking, and the resulting patterned pattern is obtained. It becomes possible to improve the heat resistance of the protective film and the shape stability against heat.

In the above formula (3), X represents an oxygen atom or a sulfur atom, R ¹ and R ² each independently represent a single bond or a divalent to tetravalent organic group, and R ⁵ and R ⁶ each independently Represents a hydrogen atom or methyl. n and m each independently represent an integer of 1 to 3. R ¹ and R ² have the same meaning as in the above formula (1).

  Examples of the compound (C) represented by the above (3) include compounds represented by the following formulas (3-1) to (3-6).

  Specific examples of the compound (C) include, for example, 1,3-bis (acryloyloxyethyl) urea, 1,3-bis (methacryloyloxyethyl) urea, 1,3-bis (methacryloyloxybutyl) urea, 1,3-bis (methacryloyloxy-2-ethoxyethyl) urea, 1,3-bis (m-methacryloyloxyphenyl) urea, 1,3-bis (1,1-bis (acryloyloxymethyl) ethyl) Examples include urea.

  (C) A compound can be used individually or in mixture of 2 or more types.

  The (C) compound can be produced, for example, by reacting an unsaturated isocyanate compound having a (meth) acryloyloxy group with water in an appropriate solvent. As an unsaturated isocyanate compound which has a (meth) acryloyloxy group, the compound similar to the unsaturated isocyanate compound used for manufacture of copolymer [A1] can be mentioned.

  Moreover, as a solvent used for manufacture of (C) compound, tetrahydrofuran, N, N- dimethylformamide, ethyl acetate, a methylene chloride etc. can be mentioned, for example.

  The amount of water used in the production of the compound (C) is preferably 50 mol% to 500 mol%, more preferably 50 mol% to the unsaturated isocyanate compound having a (meth) acryloyloxy group. 100 mol%. The compound (C) thus obtained is preferably purified by recrystallization or the like using methanol, ethanol or the like.

  In the radiation sensitive resin composition of the present invention, the amount of the compound (C) used is preferably 0.1 parts by weight to 100 parts by weight, more preferably 1 part by weight to 100 parts by weight of the component (A). 50 parts by weight, more preferably 3 to 20 parts by weight. If the amount of the compound (C) used is less than 0.1 parts by weight, the desired effect may not be obtained. On the other hand, if it exceeds 100 parts by weight, precipitates will be produced during storage of the resulting radiation-sensitive resin composition. May occur.

[(D) Compound]
The (D) compound contained in the radiation sensitive resin composition of 1st Embodiment of this invention is a compound shown by following formula (2). The radiation sensitive resin composition of this embodiment can form the cured film which shows the adhesive force outstanding with respect to the metal by containing (D) compound. And the touch panel of embodiment of this invention mentioned later can have the metal wiring etc. which were comprised with the laminated structure used as Mo / Al / Mo, for example. Therefore, the radiation sensitive resin composition of this embodiment can provide a protective film with excellent adhesion that can be suitably used for the touch panel of the embodiment of the present invention.

In the above formula (2), R ¹¹ and R ¹² represent a hydrogen atom or a methyl group. j represents an integer of 1 to 5, and k represents an integer of 1 to 2.

  Examples of commercially available products of the compound (C) represented by the above formula (2) include PM21 (manufactured by Nippon Kayaku Co., Ltd.).

  In the radiation sensitive resin composition of the present invention, the amount of the compound (D) used is preferably 0.1 parts by weight to 100 parts by weight, more preferably 10 parts by weight, with respect to 100 parts by weight of the component (A). 60 parts by weight, more preferably 30 to 50 parts by weight. (D) If the amount of the compound used is less than 0.1 parts by weight, the effect of improving the adhesion in the protective film is not sufficiently exhibited. Moreover, when it contains exceeding 100 weight part, there exists a possibility that deterioration, such as corrosion, may be accelerated | stimulated in the metal material coat | covered with the protective film formed.

[(E) Unsaturated compound having urethane bond]
The radiation-sensitive resin composition of the first embodiment of the present invention includes (A) a binder polymer, (B) a photopolymerization initiator, (C) a compound represented by the above formula (1), and (D) the above formula. In addition to the compound represented by (2), as an optional component, (E) an unsaturated compound having a urethane bond (simply referred to as (E) component or (E) compound) may be contained. .

  The radiation sensitive resin composition of this embodiment can reduce that the protective film obtained induces deterioration of metals, such as corrosion, by containing (E) compound. Moreover, the use of the compound (E) can improve the flexibility of the protective film to be formed. For example, the adhesion of the protective film to metal can be improved. And the touch panel of embodiment of this invention mentioned later can have the metal wiring etc. which were comprised with the laminated structure used as Mo / Al / Mo, for example. Therefore, the radiation sensitive resin composition of the present embodiment provides a protective film that suppresses deterioration such as corrosion of metal wiring, is flexible, exhibits excellent adhesion, and can be suitably used for the touch panel of the present embodiment. can do.

  As (E) compound which can be contained in the radiation sensitive resin composition of 1st Embodiment of this invention, what contains acrylic acid, methacrylic acid, acrylic acid ester, methacrylic acid ester, a polyol, and diisocyanate as a structural component. Used. For example, at least one monomer selected from acrylic acid, methacrylic acid, acrylic acid ester, and methacrylic acid ester, and a polyol, and at least hydroxy acrylate having one or more hydroxyl groups and hydroxy methacrylate having one or more hydroxyl groups At least one of urethane acrylate and urethane methacrylate can be produced by preparing one and reacting it with diisocyanate.

  In the radiation-sensitive resin composition of the first embodiment of the present invention, the compound (E) may be used alone or in combination of two or more.

  The acrylic acid ester, methacrylic acid ester, polyol, diisocyanate and the like described above are not particularly limited, and examples thereof include substances exemplified in paragraphs 0032 to 0034 of JP-A-2007-290341.

  Commercially available products of these unsaturated compounds having (E) urethane bond are UN-9200, UN-3320, UN-901, UN-905, UN-952, UN-5507, UN-904, UN-906AVN ( Negami Kogyo) and the like.

  The usage-amount of the (E) compound in the radiation sensitive resin composition of 1st Embodiment of this invention is not restrict | limited in particular. The use ratio of the compound (E) in the radiation sensitive resin composition of the first embodiment of the present invention is, for example, 1 part by weight to 70 parts by weight with respect to 100 parts by weight of the resin in the radiation sensitive resin composition. Preferably, it is the range of 5 weight part-45 weight part. By using in this range, it is possible to improve the effect of preventing corrosion of metals such as metal wiring and the adhesion to metal such as metal wiring at a high level.

[(F) inorganic oxide particles]
The radiation-sensitive resin composition of the first embodiment of the present invention includes (A) a binder polymer, (B) a photopolymerization initiator, (C) a compound represented by the above formula (1), and (D) the above formula. In addition to the compound represented by (2), (F) inorganic oxide particles can be contained as an optional component.

  The inorganic oxide particles (F) that are the component (F) of the radiation-sensitive resin composition of the present embodiment are contained in the radiation-sensitive resin composition, and the electrical insulation of the resulting cured film is maintained. At the same time, it is possible to control the dielectric constant, which is a dielectric characteristic. The inorganic oxide particles can also be used for the purpose of controlling the refractive index of the cured film, controlling the transparency of the cured film, suppressing cracks by alleviating curing shrinkage, and improving the surface hardness of the cured film. . That is, (F) inorganic oxide particles are used to control the relative dielectric constant, the refractive index, the transparency, the cracks, the surface hardness of the protective film obtained from the radiation-sensitive resin composition of the present embodiment. Improvements can be realized.

  The inorganic oxide particles (F) of the radiation-sensitive resin composition of the present embodiment are at least selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, indium, tin, antimony, strontium, barium, cerium, and hafnium. It is an inorganic oxide particle which is an oxide containing one element.

Among these groups, oxide particles of silicon, zirconium, titanium or zinc are preferable, and silica particles which are oxide particles of silicon, oxide particles of zirconium or titanium and barium titanate (BaTiO ₃ ) are particularly preferable. These can be used alone or in combination of two or more. The inorganic oxide particles (F) may be composite oxide particles of the above-described elements. Examples of the composite oxide particles include barium titanate and strontium titanate. Moreover, ATO (antimoy-tin oxide), ITO (indium-tin oxide), IZO (indium-zinc oxide), etc. can also be used in the range which does not impair the electrical insulation of hardened | cured material. As these inorganic oxide particles, commercially available ones such as Nanotech (registered trademark) manufactured by CI Kasei Co., Ltd. can be used.

  (F) The shape of the inorganic oxide particles is not particularly limited, and may be spherical or amorphous, and may be hollow particles, porous particles, core-shell particles, or the like. Further, the volume average particle diameter of the (F) inorganic oxide particles determined by the dynamic light scattering method is preferably 5 nm to 200 nm, more preferably 5 nm to 100 nm, and particularly preferably 10 nm to 80 nm. (F) If the volume average particle diameter of the inorganic oxide particles is less than 5 nm, the hardness of the cured film obtained using the radiation-sensitive resin composition may be reduced, or the intended relative dielectric constant may not be expressed. Yes, if it exceeds 200 nm, the haze of the cured film may increase and the transmittance may decrease, and the smoothness of the cured film may deteriorate.

  (F) Although it does not specifically limit as a compounding quantity of inorganic oxide particle, 1 mass part-500 mass parts are preferable with respect to 100 mass parts of above-mentioned (A) binder polymers, and 5 mass parts-300 mass parts are. More preferred. (F) When the compounding quantity of inorganic oxide particles is less than 1 part by mass, the above-described properties of the resulting cured film cannot be controlled within a desired range. On the other hand, if the blending amount of (F) inorganic oxide particles exceeds 500 parts by mass, the coatability and the film curability may be lowered, and the haze of the resulting protective film may be increased.

  (F) When preparing the radiation-sensitive resin composition of the present embodiment, the inorganic oxide particles are used as a powder as a component (A), a solvent as a component (G) described later, and other optional components. You may mix with a component, (F) inorganic oxide particle may be previously mixed with the solvent as a below-mentioned (G) component, and may be handled as a dispersion liquid of (F) inorganic oxide particle. Furthermore, you may handle by adding the dispersing agent as other arbitrary components to the dispersion liquid of (F) inorganic oxide particle. In addition, when (F) inorganic oxide particles are mixed with other components, it is preferable to perform a dispersion treatment in order to prevent aggregation of the (F) inorganic oxide particles and to control the particle size to be uniform.

  The dispersion treatment may be performed by using various bead mills such as a paint shaker, an SC mill, an annular mill, a pin mill, and the like until the decrease in particle size is not observed. The duration is preferably several hours. In this dispersion, it is preferable to use dispersed beads such as glass beads and zirconia beads. The bead diameter is not particularly limited, but is preferably 0.05 mm to 0.5 mm, more preferably 0.08 mm to 0.5 mm, and still more preferably 0.08 mm to 0.2 mm.

  Further, (F) the inorganic oxide particles may be controlled to have a uniform particle size by dispersing the aggregated coarse particles as described above, or the sol-gel reaction in the gas phase or in the liquid phase. Thus, the particle size-controlled (F) inorganic oxide particles or the dispersion of (F) inorganic oxide particles may be directly produced.

[(G) Solvent and other optional components]
The radiation-sensitive resin composition of the first embodiment of the present invention includes (A) a binder polymer, (B) a photopolymerization initiator, (C) a compound represented by the above formula (1), and (D) the above formula. In addition to the compound represented by (2), as an optional component, (E) an unsaturated compound having a urethane bond and (F) inorganic oxide particles can be contained, and (G) a solvent and other optional components Ingredients can be included.

  When the radiation-sensitive resin composition of the present embodiment contains (F) inorganic oxide particles, the radiation-sensitive resin composition can be uniformly (F) by further containing a dispersant as the component (G) (F). ) Inorganic oxide particles can be dispersed, and coating properties can be improved. And the radiation sensitive resin composition of this embodiment improves the adhesiveness to the board | substrate etc. of the cured film obtained using it, and characteristics, such as a dielectric constant and a refractive index, become a desired value uniformly. Can be controlled.

  (G) As a dispersing agent, a nonionic dispersing agent, a cationic dispersing agent, an anionic dispersing agent etc. can be mentioned.

  (G) Nonionic dispersants suitable for the dispersant include polyoxyethylene alkyl phosphate ester, amide amine salt of high molecular weight polycarboxylic acid, ethylenediamine propylene oxide-ethylene oxide condensate, polyoxyethylene alkyl ether, polyoxyethylene Alkyl phenol ethers, alkyl glucosides, polyoxyethylene fatty acid esters, sucrose fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters or fatty acid alkanolamides are preferred.

  As said polyoxyethylene alkyl phosphate ester, the compound represented by following formula (5) is preferable.

(In the formula ^{(5), R 31} are each _{independently, C q H 2q + 1 -CH} 2 O- (CH 2 CH 2 O) q '-CH 2 CH 2 is O-. Its q is 12-16 The q ′ is an integer of 8 to 10. The L is an integer of 1 to 3.)

  As a commercial item of the dispersant represented by the above formula (5), PLAAD ED151 manufactured by Enomoto Kasei Co., Ltd. and the like can be mentioned. According to the above polyoxyethylene alkyl phosphate ester, the uniform dispersibility of the inorganic oxide particles can be further improved.

  As the above-mentioned amidoamine salt of high molecular weight polycarboxylic acid, those represented by the following formula (6) are preferable.

(In formula (6), r and s are numbers selected such that the polystyrene-equivalent number average molecular weight determined by gel permeation chromatography is 10,000 to 40,000.)

  As a commercial item of the dispersant represented by the above formula (6), PLAAD ED211 manufactured by Enomoto Kasei Co., Ltd. and the like can be mentioned. The uniform dispersibility of the inorganic oxide particles can be further improved by the above amide amine salt of high molecular weight polycarboxylic acid.

  As the above-mentioned ethylenediaminepropylene oxide-ethylene oxide condensate, one represented by the following formula (7) is preferable.

(In formula (7), t and u are numbers selected so that the polystyrene-equivalent number average molecular weight determined by gel permeation chromatography is 1000 to 30000.)

  Examples of commercially available dispersants represented by the above formula (7) include Adeka Pluronic TR-701, TR-702, and TR-704 manufactured by ADEKA Corporation. Even with the above ethylenediaminepropylene oxide-ethylene oxide condensate, the uniform dispersibility of (F) inorganic oxide particles can be further improved.

  As said polyoxyethylene alkyl ether, what is represented by following formula (8) is preferable.

(In Formula (8), R ³⁴ is an alkyl group having 1 to 20 carbon atoms. V is an integer of 10 to 300.)

In the polyoxyethylene alkyl ether represented by the above formula (8), R ³⁴ is particularly preferably an alkyl group having 1 to 12 carbon atoms.
As a commercial item of the dispersing agent represented by the above formula (8), Adeka (trademark) TN / SO / UA series manufactured by ADEKA Corporation and the like can be mentioned.

  As the above-mentioned polyoxyethylene alkylphenol ether, a compound represented by the following formula (9) is preferable.

(In the formula ^{(9), R 35} is .w an alkyl group having 1 to 12 carbon atoms is an integer of 10 to 300.)

  Examples of commercially available dispersants represented by the above formula (9) include ADEKA Adecatol (registered trademark) SP / PC series.

  As said alkyl glucoside, what is represented by following formula (10) is preferable.

(In Formula (10), R ³⁶ , R ³⁷ , R ³⁸ , R ³⁹ and R ⁴⁰ are each independently hydrogen or an alkyl group having 1 to 12 carbon atoms.)

  As said polyoxyethylene fatty acid ester, what is represented by following formula (11) is preferable.

(In formula (11), R ⁴¹ is an alkyl group having 1 to 20 carbon atoms. R ⁴² is hydrogen or an acyl group having 2 to 13 carbon atoms. Y is an integer of 10 to 300.)

In the polyoxyethylene fatty acid ester represented by the above formula (11), R ⁴¹ is particularly preferably an alkyl group having 1 to 12 carbon atoms.

  Examples of commercially available dispersants represented by the above formula (11) include Adeka Estor (registered trademark) OEG series, Adeka Estor (registered trademark) TL series manufactured by ADEKA Corporation.

  As said sucrose fatty acid ester, what is represented by following formula (12) is preferable.

(In Formula (12), R ⁴³ , R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , R ⁴⁷ , R ⁴⁸ , R ⁴⁹ and R ⁵⁰ are each independently hydrogen or an acyl group having 2 to 13 carbon atoms.)

  As said sorbitan fatty acid ester, what is represented by following formula (13) is preferable.

(In Formula (13), R ⁵¹ is a group represented by — (CH ² CH ² O) _z1 —H. Z1 is an integer of 10 to 300.)

  As a commercial item of the dispersing agent represented by the above formula (13), Adeka Estor (registered trademark) S series manufactured by ADEKA Corporation and the like can be mentioned.

  As polyoxyethylene sorbitan fatty acid ester, what is represented by following formula (14) is preferable.

(In the formula ^{(14), R 52, R} 53 and ^{R 54} are each independently hydrogen or _{- (CH 2 CH 2 O)} .z2 a group represented by z2 -H is 10 to 300 (It is an integer.)

  As fatty acid alkanolamide, what is represented by following formula (15) is preferable.

(In the formula ^{(15), R 55} is an alkyl group having 1 to 20 carbon atoms.)

In the fatty acid alkanolamide represented by the above formula (15), R ⁵⁵ is particularly preferably an alkyl group having 1 to 12 carbon atoms.

  Examples of commercially available dispersants represented by the above formula (15) include ADEKA's Adekatol (registered trademark) series and the like.

  In the radiation sensitive resin composition of the present embodiment, the amount of the dispersant as the component (G) is not particularly limited, but when (F) inorganic oxide particles are contained, (F) inorganic oxide 0.1 mass part-100 mass parts are preferable with respect to 100 mass parts of particle | grains, and 10 mass parts-60 mass parts are more preferable. When the blending amount of the dispersant as the component (G) is less than 0.1 parts by mass, the dispersibility of the inorganic oxide particles (F) is lowered, and thereby the coating properties and storage stability of the radiation sensitive resin composition are reduced. As a result, the patterning property may decrease. On the other hand, when the blending amount exceeds 100 parts by mass, the radiation sensitive property may be deteriorated in the radiation sensitive resin composition of the present embodiment. Moreover, when there are too many dispersing agents, there exists a possibility that the adhesiveness to the board | substrate etc. of the hardened | cured material obtained using the radiation sensitive resin composition of this embodiment may fall, and heat resistant transparency may be impaired. .

  The dispersant as component (G) may be added when preparing the radiation-sensitive resin composition, and the dispersant and (F) inorganic oxide particles may be added in advance as an optional solvent as component (G). The dispersion treatment may be performed by mixing them in (F) as a dispersion of inorganic oxide particles.

  As the (G) solvent and other optional components of the radiation-sensitive resin composition of the present embodiment, a solvent, a surfactant and the like can be contained in addition to the dispersant. Hereinafter, the solvent and surfactant which are the (G) solvent and other optional components of the radiation-sensitive resin composition of the present embodiment will be described.

  The solvent which is (G) component adjusts the radiation sensitive resin composition of this embodiment to desired solid content concentration, (A) binder polymer, (B) photoinitiator, (C) said formula ( The compound represented by 1), (D) the compound represented by the above formula (2), and other optional components as the component (G) can be dissolved uniformly and stably, or (F) inorganic oxide particles can be dissolved. When contained, the (F) inorganic oxide particles can be uniformly and stably dispersed in the radiation-sensitive resin composition. Moreover, the applicability | paintability and film formability at the time of apply | coating the radiation sensitive resin composition of this embodiment to a board | substrate can be improved. That is, the solvent which is (G) component will not be specifically limited if it has the above functions.

  (G) As a solvent, alcohols such as methanol, ethanol, isopropyl alcohol, butanol, octanol; ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3- Esters such as methyl methoxypropionate and ethyl 3-ethoxypropionate; ethers such as ethylene glycol monobutyl ether, propylene glycol monomethyl ether and diethylene glycol monomethyl ether; dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, etc. Amides; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; benzene, toluene Xylene, it can be used aromatic hydrocarbons such as ethylbenzene. (G) A solvent can be used 1 type or in mixture of 2 or more types.

  The surfactant as the component (G) can be added to improve the coating property of the radiation-sensitive resin composition of the present embodiment, reduce coating unevenness, and improve the developability of the radiation irradiated portion. Examples of preferred surfactants include fluorine-based surfactants, silicone-based surfactants, and other surfactants.

  Examples of the fluorosurfactant include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether and 1,1,2,2-tetrafluorooctylhexyl. Ether, octaethylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di (1, Fluoroethers such as 1,2,2-tetrafluorobutyl) ether and hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether; sodium perfluorododecyl sulfonate; 1,1 , 2, 2, 8, 8, 9, 9, 10, 10-decafluorododecane, 1, 1, 2, 2, 3, 3 Fluoroalkanes such as hexafluorodecane; sodium fluoroalkylbenzenesulfonates; fluoroalkyloxyethylene ethers; fluoroalkylammonium iodides; fluoroalkylpolyoxyethylene ethers; perfluoroalkylpolyoxyethanols; perfluoroalkylalkoxy Rates: Fluorine alkyl esters and the like can be mentioned.

  As a commercial item of the said fluorosurfactant, it is a brand name, for example, BM-1000, -1100 (above, the product made by BM CHEMIE), MegaFac (trademark) F142D, F172, F173, F183. , F178, F191, F471, F476 (above, manufactured by DIC Corporation), Florad FC 170C, FC-171, FC-430, FC-431 (above, manufactured by Sumitomo 3M Limited) , Surflon (registered trademark) S-112, S-113, S-131, S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 (above, Asahi Glass Co., Ltd.), F-top EF301, EF303, EF352 (above, Shin-Akita Kasei Co., Ltd.) ), FT-100, FT-110, FT-140A, FT-150, FT-250, FT-251, FTX-251, FTX-218, FT- 300, FT-310, FT-400S (made by Neos Co., Ltd.) and the like.

  As said silicone type surfactant, it is a commercial item and is a brand name, for example, Toray silicone DC3PA, DC7PA, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH-190, SH-193 SZ-6032, SF-8428, DC-57, DC-190 (manufactured by Toray Dow Corning Silicone Co., Ltd.), TSF-4440, -4300, -4445, -4446 -4460, -4442 (above, manufactured by Momentive Performance Materials Japan GK).

  Examples of the other surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene n-octylphenyl ether, polyoxyethylene n -Polyoxyethylene aryl ethers such as nonylphenyl ether; nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; , KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 57, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.).

  The above-mentioned surfactants can be used alone or in admixture of two or more.

  The amount of the surfactant used is preferably 0.01 parts by mass to 10 parts by mass, more preferably 0.05 parts by mass to 5 parts by mass with respect to 100 parts by mass of the (A) binder polymer. . By making the compounding quantity of surfactant into 0.01 mass part-10 mass parts, the applicability | paintability of the radiation sensitive resin composition of this embodiment can be optimized.

  The radiation sensitive resin composition of this embodiment can contain a various additive further as needed as (G) component. Examples of the additive include an adhesion assistant, a storage stabilizer, and a heat resistance improver.

  The above-mentioned adhesion assistant is a component having a function of further improving the adhesion between the protective film formed from the radiation-sensitive resin composition of the present embodiment and the substrate on which the protective film is provided. A ring agent is preferred.

  Examples of the functional silane coupling agent include compounds having a reactive functional group such as a carboxyl group, a methacryloyl group, a vinyl group, an isocyanate group, and an epoxy group, and more specifically, trimethoxysilyl. Benzoic acid, γ-methacryloyloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ) Ethyltrimethoxysilane and the like.

  These adhesion assistants can be used alone or in admixture of two or more.

  The amount of the adhesion assistant is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, with respect to 100 parts by weight of the (A) binder polymer. When the compounding amount of the adhesion assistant exceeds 20 parts by weight, there is a tendency that a development residue at the time of development tends to occur.

  Examples of the storage stabilizer described above include sulfur, quinone compounds, hydroquinone compounds, polyoxy compounds, amines, nitronitroso compounds, and the like. More specifically, 4-methoxyphenol, N-nitroso-N- Examples include phenylhydroxylamine aluminum.

  These storage stabilizers can be used alone or in admixture of two or more.

  The amount of the storage stabilizer is preferably 3 parts by weight or less, more preferably 0.001 part by weight to 0.5 part by weight with respect to 100 parts by weight of the (A) binder polymer. When the amount of the storage stabilizer exceeds 3 parts by weight, the sensitivity may be lowered and the pattern shape may be impaired.

Examples of the heat resistance improver described above include N- (alkoxymethyl) glycoluril compounds and N- (alkoxymethyl) melamine compounds.
Examples of the N- (alkoxymethyl) glycoluril compound include N, N, N ′, N′-tetra (methoxymethyl) glycoluril, N, N, N ′, N′-tetra (ethoxymethyl) glycoluril. N, N, N ′, N′-tetra (n-propoxymethyl) glycoluril, N, N, N ′, N′-tetra (i-propoxymethyl) glycoluril, N, N, N ′, N ′ -Tetra (n-butoxymethyl) glycoluril, N, N, N ′, N′-tetra (t-butoxymethyl) glycoluril and the like can be mentioned.

  Of these N- (alkoxymethyl) glycoluril compounds, N, N, N ′, N′-tetra (methoxymethyl) glycoluril is particularly preferable.

  Examples of the N- (alkoxymethyl) melamine compound include N, N, N ′, N ′, N ″, N ″ -hexa (methoxymethyl) melamine, N, N, N ′, N ′, N ″, N ″ -hexa (ethoxymethyl) melamine, N, N, N ′, N ′, N ″, N ″ -hexa (n-propoxymethyl) melamine, N, N, N ′, N ', N ″, N ″ -hexa (i-propoxymethyl) melamine, N, N, N ′, N ′, N ″, N ″ -hexa (n-butoxymethyl) melamine, N, N, N ′, N ′, N ″, N ″ -hexa (t-butoxymethyl) melamine and the like can be mentioned.

  Among these N- (alkoxymethyl) melamine compounds, N, N, N ′, N ′, N ″, N ″ -hexa (methoxymethyl) melamine is particularly preferable. Examples thereof include Nicalac (registered trademark) N-2702, MW-30M (manufactured by Sanwa Chemical Co., Ltd.), and the like.

  These heat resistance improvers can be used alone or in admixture of two or more.

  The blending amount of the heat resistance improver is preferably 30 parts by weight or less, more preferably 20 parts by weight or less, relative to parts by weight of the (A) binder polymer. When the blending amount of the heat resistance improver exceeds 30 parts by weight, the storage stability of the radiation sensitive resin composition tends to be lowered.

<Preparation of radiation-sensitive resin composition>
The radiation sensitive resin composition of the present embodiment includes the above-described (A) binder polymer, (B) photopolymerization initiator, (C) the compound represented by the above formula (1), and (D) the above formula (2). It is prepared by mixing the indicated compounds at a predetermined ratio.

  Moreover, the radiation sensitive resin composition of this embodiment contains the (E) unsaturated compound which has a urethane bond, the (F) inorganic oxide particle, the (G) solvent, and other arbitrary components as needed. In this case, (E) an unsaturated compound having a urethane bond, (F) inorganic oxide particles, (G) a solvent and other optional components are mixed at a predetermined ratio. (A) The binder polymer may be preliminarily dissolved in a solvent and handled as a (A) binder polymer solution. (B) Essential components such as a photopolymerization initiator are preliminarily dissolved in a solvent, and (B) It may be handled as a solution of a photopolymerization initiator or the like, and (F) inorganic oxide particles may be handled as a dispersion liquid of (F) inorganic oxide particles as described above, or any other (G) component The components may be dissolved in a solvent in advance and handled as a solution of (G) other optional components. As the solvent used in these cases, the same solvent as the above-mentioned (G) solvent can be used. Moreover, when it contains (F) inorganic oxide particle | grains, you may perform a dispersion | distribution process as needed as above-mentioned.

Embodiment 2. FIG.
<Photosensitive dry film>
The radiation sensitive resin composition of 1st Embodiment of this invention mentioned above can be used conveniently for formation of the protective film of the touchscreen of embodiment of this invention mentioned later. In that case, the radiation-sensitive resin composition of the first embodiment of the present invention is directly applied to a substrate on which metal wiring or the like for forming a touch panel is formed, followed by drying, patterning (exposure and development). Etc.) and, if necessary, curing can be carried out to form a protective film having a desired shape.

  And in forming the protective film of a touch panel using the radiation sensitive resin composition of this embodiment, the photosensitive dry film of this invention is formed from a radiation sensitive resin composition as a more preferable method, The book The method of forming a protective film using the photosensitive dry film of invention can be mentioned.

  Hereinafter, the photosensitive dry film of the embodiment of the present invention formed using the radiation sensitive resin composition of the embodiment of the present invention, and the radiation sensitive resin layer serving as a protective film using the photosensitive dry film The laminating method will be described.

  FIG. 1 is a schematic cross-sectional view showing a photosensitive dry film according to a second embodiment of the present invention.

  As shown in FIG. 1, the photosensitive dry film 100 according to the second embodiment of the present invention includes a support film 101, a radiation-sensitive resin layer 102 formed on the support film 101, and a radiation-sensitive resin layer 102. And a protective film 103 disposed on the top. The radiation sensitive resin layer 102 is formed on the support film 101 using the radiation sensitive resin composition of the first embodiment of the present invention described above.

  More specifically, in the formation of the photosensitive dry film 100 according to the second embodiment of the present invention, the radiation-sensitive resin composition according to the first embodiment of the present invention described above is used and applied onto the support film 101. And dried to form the radiation sensitive resin layer 102. Subsequently, the photosensitive dry film 100 is formed by bonding the protective film 103 on the radiation sensitive resin layer 102. Therefore, the photosensitive dry film 100 of 2nd Embodiment of this invention can be formed using the radiation sensitive resin composition of 1st Embodiment of this invention mentioned above.

  In addition, the photosensitive dry film of 2nd Embodiment of this invention can also be set as the structure which does not provide a protective film on the radiation sensitive resin layer on a support film as another example. That is, another example of the photosensitive dry film according to the second embodiment of the present invention may have a structure including a support film and a radiation-sensitive resin layer, unlike the photosensitive dry film 100 shown in FIG. .

  Examples of the support film 101 of the photosensitive dry film 100 include films made of polyethylene terephthalate, polycarbonate, polyethylene, polypropylene, polyethersulfone, and the like. Specific examples include polyester films such as Teijin Tetron film GS series and DuPont Mylar film D series. And preferably, a polyethylene terephthalate film is used.

  The thickness of the support film 101 is preferably about 5 μm to 100 μm, and more preferably 10 μm to 70 μm in order to ensure coverage and perform exposure through the support film with high efficiency.

  As described above, the radiation-sensitive resin layer 102 of the photosensitive dry film 100 is formed using the radiation-sensitive resin composition of the first embodiment of the present invention.

  Examples of the protective film 103 include polyethylene, polypropylene, polyethylene terephthalate, polycarbonate, polyethylene-vinyl acetate copolymer, and a film having a thickness of about 5 μm to 100 μm made of a laminated film of polyethylene-vinyl acetate copolymer and polyethylene. It is done.

  The photosensitive dry film 100 of 2nd Embodiment of this invention is used in order to laminate | stack the radiation sensitive resin layer 102 which consists of the radiation sensitive resin composition of 1st Embodiment of this invention mentioned above on a sample. Can do.

  For example, in manufacturing a touch panel according to an embodiment of the present invention to be described later, on a touch panel substrate having a detection electrode and a metal wiring having a laminated structure of, for example, Mo / Al / Mo. The radiation sensitive resin layer 102 can be laminated. A protective film can be formed from the disposed radiation-sensitive resin layer 102 through a patterning process such as exposure and development.

  As a method of laminating the radiation-sensitive resin layer 102 on a sample such as a touch panel substrate using the photosensitive dry film 100, the radiation-sensitive resin layer 102 adheres to the sample while removing the protective film 103. Thus, it can implement by laminating. More specifically, after removing the protective film 103 from the photosensitive dry film 100, while heating the remaining photosensitive dry film 100, for example, on the surface of the sample such as a substrate surface of a touch panel provided with metal wiring, The radiation sensitive resin layer 102 is pressure bonded. As a result, the radiation sensitive resin layer 102 can be laminated on the above-described sample.

  The heating temperature at the time of pressure bonding is preferably 10 ° C. to 180 ° C., more preferably 20 ° C. to 160 ° C., and 30 ° C. to 150 ° C. so that the radiation sensitive resin layer 102 is not thermally deteriorated. More preferably.

Moreover, as a pressure-bonding means at the time of pressure bonding, it is preferable to use a pressure-bonding roll. The crimping pressure, from the viewpoint of suppressing the deformation of the sample, a linear pressure, it is preferable that the ^{50N / m~1 × 10 5 N /} m, 2.5 × 10 2 N / m~5 × 10 4 N / M is more preferable, and 5 × 10 ² N / m to ⁴ × 10 ⁴ N / m is even more preferable.

  According to the above method, the photosensitive dry film 100 according to the second embodiment of the present invention is formed by laminating the radiation-sensitive resin layer 102 made of the above-described radiation-sensitive resin composition according to the first embodiment of the present invention on a sample. can do. And the radiation sensitive resin layer 102 can form a protective film through patterning processes, such as exposure and image development, and the further exposure process and heat processing as needed.

Embodiment 3 FIG.
<Touch panel>
The touch panel which is 3rd Embodiment of this invention is a touch panel which has metal wiring and the protective film which covers at least one part of the metal wiring. That is, the touch panel of the present embodiment has detection electrodes for detecting a touch operation such as an operator's finger on the substrate. And the touch panel of this embodiment has the wiring electrically connected to a detection electrode, The wiring is the metal wiring formed using the metal material. In the touch panel of the present embodiment, the wiring connected to the detection electrode includes a wiring for routing the detection electrode to the end portion of the touch panel substrate, and includes a wiring for connecting portions of the separated detection electrodes. . The touch panel according to the present embodiment includes a protective film that covers and protects these wirings.

  The touch panel of the present embodiment can be a capacitive touch panel, for example.

  FIG. 2 is a plan view showing a touch panel according to a third embodiment of the present invention.

  FIG. 3 is a sectional view taken along line B-B ′ of FIG. 2.

  As shown in FIG. 2, the touch panel 21 of the present embodiment includes a first detection electrode 23 extending in the X direction and a second detection electrode extending in the Y direction orthogonal to the X direction on the surface of the transparent substrate 22. 24.

  The transparent substrate 22 can be a glass substrate. The transparent substrate 22 can also be a resin substrate. In that case, a polyethylene terephthalate film, a polybutylene terephthalate film, a polyethylene film, a polypropylene film, a polyethersulfone film, a polycarbonate film, a polyacryl film, a polyvinyl chloride film, A polyimide film, a ring-opened polymer film of cyclic olefin, a film made of a hydrogenated product thereof, and the like can be used. The thickness of the transparent substrate 22 can be 0.1 mm to 3 mm in the case of a glass substrate. In the case of a resin substrate, it can be 10 μm to 3000 μm.

  A plurality of first detection electrodes 23 and second detection electrodes 24 are arranged. The first detection electrodes 23 and the second detection electrodes 24 are arranged in a matrix in the operation area of the touch panel 21. The first detection electrode 23 is used to detect the coordinate in the Y direction of the touch position by the operator. The second detection electrode 24 is used to detect the coordinate in the X direction of the touch position by the operator. The first detection electrode 23 and the second detection electrode 24 are provided in the same layer on the same surface of the transparent substrate 22. The number of the first detection electrodes 23 and the second detection electrodes 24 is not limited to the example shown in FIG. 2, but is preferably determined according to the size of the operation area and the required touch position detection accuracy. . That is, the touch panel 21 can be configured by using a larger number or a smaller number of the first detection electrodes 23 and the second detection electrodes 24.

  As shown in FIG. 2, each of the first detection electrode 23 and the second detection electrode 24 includes a plurality of rhomboid electrode pads 30. The first detection electrode 23 and the second detection electrode 24 are arranged such that the electrode pad 30 of the first detection electrode 23 is separated from the electrode pad 30 of the second detection electrode 24 adjacent thereto. At this time, the gap between the electrode pads 30 is very small enough to ensure insulation.

And the 1st sensing electrode 23 and the 2nd sensing electrode 24 are arrange | positioned so that the part which mutually cross | intersects can be made as small as possible. Then, the electrode pads 30 constituting the first detection electrode 23 and the second detection electrode 24 are arranged over the entire operation area of the touch panel 21.
As shown in FIG. 2, the electrode pad 30 can have a rhombus shape, but is not limited to this shape, and can be a polygonal shape such as a hexagon.

  Each of the first detection electrode 23 and the second detection electrode 24 is preferably a transparent electrode. Here, the transparent electrode is an electrode having high transparency to visible light. As the first detection electrode 23 and the second detection electrode 24, an electrode made of a transparent conductive material such as an electrode made of ITO or an electrode made of indium oxide and zinc oxide can be used. When the 1st sensing electrode 23 and the 2nd sensing electrode 24 consist of ITO, respectively, it is preferable that those thickness shall be 10 nm-100 nm so that sufficient electroconductivity can be ensured.

  The first detection electrode 23 and the second detection electrode 24 can be formed using a known method. For example, a film made of a transparent conductive material such as ITO is formed using a sputtering method or the like, and photolithography is performed. This can be done by patterning using a method or the like.

  As shown in FIGS. 2 and 3, the first detection electrode 23 and the second detection electrode 24 are formed on the same surface of the transparent substrate 22 and form the same layer. Therefore, the first detection electrode 23 and the second detection electrode 24 intersect at a plurality of locations in the operation region, and form an intersection 28.

  As shown in FIG. 3, the touch panel 21 according to the present embodiment is divided at the intersection 28 so that one of the first detection electrode 23 and the second detection electrode 24 does not contact the other. That is, the first detection electrode 23 is connected at the intersection 28, but the second detection electrode 24 extending in the left-right direction in FIG. 3 is divided and formed. A bridge wiring 32 is provided to electrically connect the disconnected portion of the second detection electrode 24. An interlayer insulating film 29 made of an insulating material is provided between the bridge wiring 32 and the first detection electrode 23.

As shown in FIG. 3, the interlayer insulating film 29 provided on the first detection electrode 23 at the intersecting portion 28 is formed of a material having excellent light transmittance. The interlayer insulating film 29 can be formed by coating using a printing method such as polysiloxane, acrylic resin, and acrylic monomer, patterning as necessary, and then heat-curing it. When formed using polysiloxane, the interlayer insulating film 29 is an inorganic insulating layer made of silicon oxide (SiO ₂ ). Further, when an acrylic resin and an acrylic monomer are used, the interlayer insulating film 29 is an organic insulating layer made of resin. In the case where SiO ₂ is used for the interlayer insulating film 29, for example, the SiO ₂ film is formed only on the first detection electrodes 23 at the intersections 28 by a sputtering method using a mask to form the interlayer insulating film 29. You can also

  On the upper layer of the interlayer insulating film 29, a bridge wiring 32 is provided. As described above, the bridge wiring 32 fulfills the function of electrically connecting the second detection electrodes 24 that are interrupted at the intersection 28. The bridge wiring 32 is preferably formed of a material having excellent light transmittance such as ITO. Further, the bridge wiring 32 can be configured by using a metal material having excellent resistance characteristics to be a metal wiring. By making the bridge wiring 32 a metal wiring having excellent resistance characteristics, the line width can be reduced and the operator of the touch panel 21 can be made inconspicuous. In the touch panel 21, the second detection electrode 24 can be electrically connected in the Y direction by providing the bridge wiring 32.

  As shown in FIG. 3, the first detection electrode 23 and the second detection electrode 24 have a shape in which a plurality of rhomboid electrode pads 30 are arranged vertically or horizontally as described above. In the first detection electrode 23, the connection portion located at the intersection 28 has a shape narrower than the rhomboid electrode pad 30 of the first detection electrode 23. The bridge wiring 32 is also narrower than the rhombic electrode pad 30 and is formed in a strip shape.

  Terminals (not shown) are provided at the ends of the first detection electrode 23 and the second detection electrode 24 of the touch panel 21, and the wirings 31 are drawn from the terminals, respectively. The wiring 31 can be a metal wiring using aluminum, copper, molybdenum, a copper-manganese alloy, or the like. Further, for example, a metal wiring formed by using a metal film of molybdenum and aluminum and forming a laminated structure of Mo / Al / Mo can be obtained.

  The wiring 31 is connected to an external control circuit (not shown) that detects the position of a voltage application or touch operation to the first detection electrode 23 and the second detection electrode 24 using a connection terminal (not shown) at the end thereof. Electrically connected.

  As shown in FIGS. 2 and 3, a light-transmitting protective film 25 is provided on the surface of the transparent substrate 22 on which the first detection electrode 23, the second detection electrode 24 and the wiring 31 are formed so as to cover the wiring 31. Is provided. Similarly, the protective film 25 is formed so as to cover the first detection electrode 23 and the second detection electrode 24. Therefore, when the bridge wiring 32 is a metal wiring like the wiring 31, the protective film 25 can cover the bridge wiring 32 that is a metal wiring as well as the wiring 31.

  The protective film 25 is patterned so as to cover and protect at least a part of the wiring 31 in the wiring formation region of the touch panel 21 and to cover and protect the first detection electrode 23 and the second detection electrode 24 in the operation region. To be formed. Specifically, the protective film 25 is formed by patterning so that connection terminals (not shown) at the ends of the wirings 31 drawn from the first detection electrode 23 and the second detection electrode 24 are exposed.

  For the formation of the protective film 25, the above-described photosensitive dry film of the second embodiment of the present invention formed using the radiation-sensitive resin composition of the first embodiment of the present invention can be used. That is, the sensitivity formed from the radiation-sensitive resin composition of the first embodiment of the present invention according to the method for laminating the radiation-sensitive resin layer described above using the photosensitive dry film of the second embodiment of the present invention. A radiation resin layer is laminated on the transparent substrate 22 of the touch panel 21. Next, the protective film 25 can be formed by performing desired patterning or the like.

  A method for forming the protective film 25 will be described in more detail below.

  First, a photosensitive dry film of the second embodiment of the present invention similar to that shown in FIG. 1 is prepared.

  Next, while removing the protective film using the photosensitive dry film, a radiation-sensitive resin layer is formed on the surface of the transparent substrate 22 on which the first detection electrode 23, the second detection electrode 24, the wiring 31, and the like are formed. Laminate in close contact. About the specific method of lamination, it is preferable to follow the method of laminating | stacking the radiation sensitive resin layer mentioned above. As a result, the radiation sensitive resin layer possessed by the photosensitive dry film is laminated on the surface of the transparent substrate 22 where the wiring 31 and the like are formed.

  Next, at least a part of the radiation-sensitive resin layer on the transparent substrate 22 is irradiated with radiation (hereinafter also referred to as exposure). In this case, when exposing a part of the radiation sensitive resin layer, the exposure is usually performed through a photomask having a predetermined pattern suitable for forming the protective film 25 of the touch panel 21. Examples of radiation used for exposure include visible light, ultraviolet light, far ultraviolet light, electron beams, and X-rays. Among these radiations, radiation having a wavelength in the range of 190 to 450 nm is preferable, and radiation containing ultraviolet light of 365 nm is particularly preferable.

The exposure amount when exposing a part of the radiation-sensitive resin layer is preferably 100 J / m ² as a value obtained by measuring the intensity of radiation at a wavelength of 365 nm with an illuminometer (OAI model 356, manufactured by OAI Optical Associates Inc.). ~10000J / ^{m 2,} more preferably ^{500J / m 2 ~6000J / m 2} .

  Next, the exposed radiation-sensitive resin layer is developed to remove unnecessary portions (when the radiation-sensitive resin layer made of the radiation-sensitive resin composition is a negative type, a non-irradiated portion). Then, a predetermined pattern is formed, and a cured film patterned into a desired shape is obtained.

  The developer used for development is preferably an alkali developer made of an aqueous solution of an alkali (basic compound). Examples of alkalis include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia; quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide. be able to.

  In addition, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant can be added to such an alkaline developer. The concentration of alkali in the alkali developer is preferably from 0.1% by mass to 5% by mass from the viewpoint of obtaining appropriate developability. As a developing method, for example, an appropriate method such as a liquid piling method, a dipping method, a rocking dipping method, a shower method, or the like can be used. The development time varies depending on the composition of the radiation sensitive resin composition, but is preferably about 10 seconds to 180 seconds. Following such development processing, for example, after washing with running water for 30 seconds to 90 seconds, a desired pattern can be formed by, for example, air drying with compressed air or compressed nitrogen.

  In addition, after development, the cured film may be further cured by further exposure as necessary. Moreover, you may heat-process at 80 to 280 degreeC instead of exposure after image development, or together with exposure.

  The thickness of the protective film 25 is preferably 0.1 μm to 8 μm, more preferably 0.1 μm to 6 μm, and still more preferably 0.1 μm to 4 μm.

  The cured film patterned to have a desired shape on the transparent substrate 22 in this way has high transparency, and is coated so as to protect the wiring 31, the first detection electrode 23, etc. A protective film 25 is formed.

  The protective film 25 is formed using the photosensitive dry film of the second embodiment of the present invention, and by extension, is formed from the radiation-sensitive resin composition of the first embodiment of the present invention. Therefore, the protective film 25 is excellent in light transmittance, and has excellent adhesion to the wiring 31 that is a metal wiring formed on the transparent substrate 22 of the touch panel. Further, the protective film 25 can suppress the deterioration of corrosion and the like in the wiring 31 from being accelerated.

  Therefore, the touch panel 21 can achieve high reliability by having the protective film 25.

  In addition, the touch panel 21 on which the protective film 25 is formed has an adhesive layer (illustrated) made of, for example, an acrylic transparent adhesive on the formation surface of the wiring 31 of the transparent substrate 22 and the first detection electrode 23 and the second detection electrode 24. A cover film (not shown) made of a transparent resin can be provided.

  The touch panel 21 having the above configuration measures capacitance in an operation region in which the first detection electrodes 23 and the second detection electrodes 24 are arranged in a matrix, and when there is a touch operation such as an operator's finger. The contact position of a finger or the like can be detected from the change in capacitance that occurs. The touch panel 21 is connected via a wiring 31 that is electrically connected to the first detection electrode 23 and the second detection electrode 24, and is placed on a display such as a liquid crystal display element or an organic EL element. It can be suitably used as an input device for the display.

  EXAMPLES Hereinafter, although embodiment of this invention is described in detail based on an Example, this invention is not interpreted limitedly by this Example.

<Preparation of radiation-sensitive resin composition>
Synthesis example 1
[Synthesis of binder polymer]
In a flask, methacrylic acid (19 w%), 2-hydroxyethyl methacrylate (19 w%), benzyl methacrylate (44 w%), cyclohexyl maleimide (10 w%), P-isopropenyl phenol (8 w%), azobisisobutyronitrile (4 w%), pentaerythritol tetrakis (3-mercaptobutyrate) (2 w%) was added, and methyl 3-methoxypropionate was added so that the S / M ratio was 2. The mixture was stirred at room temperature under a nitrogen atmosphere to dissolve all the monomers, and then reacted at 90 ° C. under a nitrogen atmosphere. After 4 hours from the start of the reaction, P-methoxyphenol was charged and added in an amount of 0.1 w% based on the total amount, and nitrogen was stopped and Air bubbling was started. Ten minutes later, 2-hydroxyethyl methacrylate and equimolar 2-isocyanatoethyl methacrylate were added dropwise using a dropping funnel. The reaction was terminated by cooling 1.5 hours after the completion of dropping to obtain a binder polymer.

Synthesis example 2
[Synthesis of (C) Compound]
A flask equipped with a condenser and a stirrer was charged with 10 parts of 2-methacryloyloxyethyl isocyanate and 30 parts of tetrahydrofuran. Subsequently, 2 parts of distilled water was added, the temperature of the solution was raised to 40 ° C., and the mixture was gently stirred for 1 hour. After removing tetrahydrofuran and distilled water by distillation under reduced pressure, recrystallization from 50 parts of ethanol gave 1,3-bis (methacryloyloxyethyl) urea of the above formula (3-1) as needle-like white crystals. It was.
It was confirmed by ¹ H-NMR that the obtained compound was 1,3-bis (methacryloyloxyethyl) urea (3-1) using heavy DMSO as a solvent and TMS as a reference. The measurement result of ¹ H-NMR is shown below. Chemical shift (proton ratio, splitting); 1.82 (3H, s), 3.26 (2H, q), 3.99 (2H, t), 5.61 (1H, s), 6.00 (1H , S), 6.08 (1H, t).

Preparation Example 1
[(F) Preparation of dispersion of inorganic oxide particles]
30 parts by weight of UEP-100 (Daiichi Rare Element Co., Ltd.), which is a powder of ZrO ₂ , 2.5 parts by weight of acidic dispersant S55000 (manufactured by Nihon Lubrizol Co., Ltd.) and a carboxylic acid moiety 2.5 parts by mass of functional acrylate Aronix (registered trademark) M-520 (manufactured by Toagosei Co., Ltd.) was added. 65 parts by mass of propylene glycol monomethyl ether (PGME) was added as a solvent, 0.1 mm zirconia beads were added 3.5 times the charged weight, sealed and lightly stirred to blend the solvent, particles and organic components. . This was set in a paint shaker and dispersed for 3 hours, and the zirconia beads were removed with a mesh filter to obtain a dispersion of (F) inorganic oxide particles.

[Preparation of radiation-sensitive resin composition]
The detail of each component used in the Example is shown below.

(A) Binder polymer (component (A))
Binder polymer according to Synthesis Example 1 above

(B) Photopolymerization initiator (component (B))
Irgacure (registered trademark) OXE02 (manufactured by BASF)

(C) Compound represented by the above formula (1) (component (C))
1,3-bis (methacryloyloxyethyl) urea (3-1)

(D) Compound represented by the above formula (2) (component (D))
D-1: Kaymer (registered trademark) PM-21 (manufactured by Nippon Kayaku Co., Ltd.)
D-2: Light ester P-2M (manufactured by Kyoeisha Chemical Co., Ltd.)
D-3: JPA-514 (Johoku Chemical Co., Ltd.)

(E) Unsaturated compound having urethane bond (component (E))
E-1: UN-906AVN (Negami Kogyo Co., Ltd.)
E-2: UN-5507 (Negami Kogyo Co., Ltd.)
E-3: UN-904 (manufactured by Negami Industrial Co., Ltd.)

(F) Dispersion of inorganic oxide particles (component (F))
Dispersion of inorganic oxide particles according to Preparation Example 1 above

Example 1
(A) The solid content of the binder polymer is 100 parts by mass, 3 parts by mass of (B) photopolymerization initiator: Irgacure (registered trademark) OXE02 (manufactured by BASF), and 1,3-bis which is component (C) (Methacryloyloxyethyl) urea (3-1) 10 parts by mass, (D) component Kayamer (registered trademark) PM-21 (manufactured by Nippon Kayaku Co., Ltd.) 40 masses, (E) component UN- 906AVN (manufactured by Negami Kogyo Co., Ltd.) is added to 100 parts by mass, and the inorganic oxide particles according to Preparation Example 1 as component (F) are added in an amount of 500 parts by mass, so that the solids concentration is 35%. Diluted with propylene glycol monomethyl ether and stirred until all the raw materials were dissolved to obtain a radiation sensitive resin composition.

Example 2
(A) The solid content of the binder polymer is 100 parts by mass, 3 parts by mass of (B) photopolymerization initiator: Irgacure (registered trademark) OXE02 (manufactured by BASF), and 1,3-bis which is component (C) (Methacryloyloxyethyl) urea (3-1) 10 parts by mass, (D) component Kayamer (registered trademark) PM-21 (manufactured by Nippon Kayaku Co., Ltd.) 40 masses, (E) component UN- 5507 (manufactured by Negami Kogyo Co., Ltd.) and 500 parts by mass of the inorganic oxide particles according to Preparation Example 1 as component (F) are added in a solid content so that the solid content concentration is 35%. Diluted with propylene glycol monomethyl ether and stirred until all the raw materials were dissolved to obtain a radiation sensitive resin composition.

Example 3
(A) The solid content of the binder polymer is 100 parts by mass, 3 parts by mass of (B) photopolymerization initiator: Irgacure (registered trademark) OXE02 (manufactured by BASF), and 1,3-bis which is component (C) (Methacryloyloxyethyl) urea (3-1) 10 parts by mass, (D) component Kayamer (registered trademark) PM-21 (manufactured by Nippon Kayaku Co., Ltd.) 40 masses, (E) component UN- Add 904 (manufactured by Negami Kogyo Co., Ltd.) to 100 parts by mass, and add 500 parts by mass of inorganic oxide particles according to Preparation Example 1 as component (F), so that the solids concentration is 35%. Diluted with propylene glycol monomethyl ether and stirred until all the raw materials were dissolved to obtain a radiation sensitive resin composition.

Example 4
(A) The solid content of the binder polymer is 100 parts by mass, 3 parts by mass of (B) photopolymerization initiator: Irgacure (registered trademark) OXE02 (manufactured by BASF), and 1,3-bis which is component (C) (Methacryloyloxyethyl) urea (3-1) 10 parts by mass, (D) component light ester P-2M (manufactured by Kyoeisha Chemical Co., Ltd.) 40 masses, (E) component UN-906AVN (Negami Kogyo) 100 parts by mass) and 500 parts by mass of the inorganic oxide particles according to Preparation Example 1 as component (F) in solid content, and propylene glycol monomethyl ether so that the solid content concentration is 35% And the mixture was stirred until all the raw materials were dissolved to obtain a radiation sensitive resin composition.

Example 5
(A) The solid content of the binder polymer is 100 parts by mass, 3 parts by mass of (B) photopolymerization initiator: Irgacure (registered trademark) OXE02 (manufactured by BASF), and 1,3-bis which is component (C) (Methacryloyloxyethyl) urea (3-1) 10 parts by mass, (D) component light ester P-2M (Kyoeisha Chemical Co., Ltd.) 40 masses, (E) component UN-5507 (Negami Kogyo) 100 parts by mass) and 500 parts by mass of the inorganic oxide particles according to Preparation Example 1 as component (F) in solid content, and propylene glycol monomethyl ether so that the solid content concentration is 35% And the mixture was stirred until all the raw materials were dissolved to obtain a radiation sensitive resin composition.

Example 6
(A) The solid content of the binder polymer is 100 parts by mass, 3 parts by mass of (B) photopolymerization initiator: Irgacure (registered trademark) OXE02 (manufactured by BASF), and 1,3-bis which is component (C) (Methacryloyloxyethyl) urea (3-1) 10 parts by mass, (D) component light ester P-2M (manufactured by Kyoeisha Chemical Co., Ltd.) 40 masses, (E) component UN-904 (Negami Kogyo) 100 parts by mass) and 500 parts by mass of the inorganic oxide particles according to Preparation Example 1 as component (F) in solid content, and propylene glycol monomethyl ether so that the solid content concentration is 35% And the mixture was stirred until all the raw materials were dissolved to obtain a radiation sensitive resin composition.

Example 7
(A) The solid content of the binder polymer is 100 parts by mass, 3 parts by mass of (B) photopolymerization initiator: Irgacure (registered trademark) OXE02 (manufactured by BASF), and 1,3-bis which is component (C) (Methacryloyloxyethyl) urea (3-1) 10 parts by mass, (D) component JPA-514 (Johoku Chemical Co., Ltd.) 40 masses, (E) component UN-906AVN (Negami Kogyo Co., Ltd.) ) And 100 parts by weight of inorganic oxide particles according to Preparation Example 1 as component (F) are added in a solid content of 500 parts by weight, and diluted with propylene glycol monomethyl ether so that the solid content concentration is 35%. And it stirred until all the raw materials melt | dissolved, and the radiation sensitive resin composition was obtained.

Example 8
(A) The solid content of the binder polymer is 100 parts by mass, 3 parts by mass of (B) photopolymerization initiator: Irgacure (registered trademark) OXE02 (manufactured by BASF), and 1,3-bis which is component (C) (Methacryloyloxyethyl) urea (3-1) 10 parts by mass, (D) component JPA-514 (Johoku Chemical Co., Ltd.) 40 masses, (E) component UN-5507 (Negami Kogyo Co., Ltd.) ) And 100 parts by weight of inorganic oxide particles according to Preparation Example 1 as component (F) are added in a solid content of 500 parts by weight, and diluted with propylene glycol monomethyl ether so that the solid content concentration is 35%. And it stirred until all the raw materials melt | dissolved, and the radiation sensitive resin composition was obtained.

Example 9
(A) The solid content of the binder polymer is 100 parts by mass, 3 parts by mass of (B) photopolymerization initiator: Irgacure (registered trademark) OXE02 (manufactured by BASF), and 1,3-bis which is component (C) (Methacryloyloxyethyl) urea (3-1) 10 parts by mass, (D) component JPA-514 (Johoku Chemical Co., Ltd.) 40 masses, (E) component UN-904 (Negami Kogyo Co., Ltd.) ) And 100 parts by weight of inorganic oxide particles according to Preparation Example 1 as component (F) are added in a solid content of 500 parts by weight, and diluted with propylene glycol monomethyl ether so that the solid content concentration is 35%. And it stirred until all the raw materials melt | dissolved, and the radiation sensitive resin composition was obtained.

<Evaluation of protective film>
Example 10
Using each of the radiation-sensitive resin compositions obtained in Examples 1 to 9, a photosensitive dry film composed of a support film and a radiation-sensitive resin layer was formed, and then protected using each photosensitive dry film. A film was formed and each protective film was evaluated.
The evaluation is performed for patterning property, water permeability (also referred to as moisture permeability), adhesion, hardness, and adhesion after a pressure cooker test (PCT). The evaluation method is described below, and the evaluation results are as follows. The summary is shown in Table 1.

[Evaluation of patterning properties]
A bar coater (Tester Sangyo AUTO FILM APPLICATOR) was prepared so that the radiation-sensitive resin composition prepared in Examples 1 to 9 was cured on the untreated surface of a polyethylene terephthalate (PET) film as a support film so that the film thickness would be 8 μm after curing. ) And prebaked in a clean oven at 100 ° C./2 minutes to remove the solvent and form a dry film. And the photosensitive dry film in which the radiation sensitive resin layer was formed on the support film was formed.

  Using this photosensitive dry film, the radiation sensitive resin layer was transferred onto a copper substrate with a laminator (Taisei Laminator FIRST LAMINATOR VAII-700 special type) whose roll temperature was set to 90 ° C., and then a UV exposure machine. Using a (TOPCON Deep-UV exposure machine TME-400PRJ), mask exposure (60 mJ) was performed using a mask having a line-and-space pattern in which 90 μm-width lines and 100 μm-width spaces were alternately arranged. Next, the PET film of the photosensitive dry film is peeled off, and the substrate on which the radiation-sensitive resin layer of the photosensitive dry film is transferred is alkali-developed with a 2% aqueous sodium carbonate solution for 50 seconds, and then rinsed with ultrapure water for 60 seconds. Then, the unexposed part was removed. This substrate was post-exposed (250 mJ), and the radiation-sensitive resin layer was further cured by post-baking (140 degrees / 25 minutes) to obtain a protective film as a patterned cured film.

  Regarding the evaluation of patterning property, the case where a mask pattern consisting of a 90 μm line and a 100 μm space can be formed without any residue is judged as “good”, and a residual remains or the formed pattern is compared with the mask pattern. The case where it became remarkably thick was judged as "bad (x)".

[Evaluation of moisture permeability]
Using the radiation sensitive resin composition of Example 1 to Example 9, using an applicator, it was applied to the untreated surface of the PET film as a support film so that the film thickness after curing was 40 μm, and in a clean oven Pre-baking was performed at 100 ° C. for 2 minutes to remove the solvent and form a dry film. And the photosensitive dry film in which the radiation sensitive resin layer was formed on the support film was formed.

  This photosensitive dry film was fully exposed (60 mJ) with a UV exposure machine (TOPCON Deep-UV exposure machine TME-400PRJ), alkali-developed with a 2% aqueous sodium carbonate solution for 50 seconds, and then rinsed with ultrapure water for 60 seconds. . This photosensitive dry film was post-exposed (250 mJ), then the radiation-sensitive resin layer was further cured by post-baking (140 degrees / 25 minutes), and the protective film was peeled off as a cured film from the PET film and taken out.

Using this protective film, moisture permeability was measured as a moisture permeability after exposure by a moisture permeability cup method. The moisture permeable cup used was “Moisture permeable cup (screw tightening type) JIS Z0208” manufactured by Imoto Seisakusho. Using calcium chloride (for moisture measurement) from Kanto Chemical Co., Ltd. as a hygroscopic agent, a moisture permeable cup obtained by measuring 5 g of this hygroscopic agent is covered with a cured film of the above-mentioned dry film, fixed with an instrument, and the cup is then cured with the cured film. The sample was completely sealed, allowed to stand at a constant temperature and humidity of 65 ° C./90% RH for 24 hours (h), and the moisture permeability was calculated from the change in the weight of the moisture absorbent before and after the test. The moisture permeability calculation formula is as follows.
Moisture permeability ^(g / m 2 · 24h)
= (Weight change amount of hygroscopic agent [g] × 24) / (moisture permeable area [m ² ] × test time [h])

[Evaluation of adhesion]
A bar coater (Tester Sangyo AUTO FILM APPLICATOR) was prepared so that the radiation-sensitive resin composition prepared in Examples 1 to 9 was cured on the untreated surface of a polyethylene terephthalate (PET) film as a support film so that the film thickness would be 8 μm after curing. ) And prebaked in a clean oven at 100 ° C./2 minutes to remove the solvent and form a dry film. And the photosensitive dry film in which the radiation sensitive resin layer was formed on the support film was formed.

  Using this photosensitive dry film, the radiation-sensitive resin layer was coated with a laminator (Taisei Laminator FIRST LAMINATOR VAII-700 special type) whose roll temperature was set to 90 ° C., and the surface of the glass substrate was coated with ITO. After the transfer onto the substrate, the entire surface was exposed (60 mJ) with a UV exposure machine (TOPCON Deep-UV exposure machine TME-400PRJ). Next, the PET film of the photosensitive dry film is peeled off, and the substrate on which the radiation-sensitive resin layer of the photosensitive dry film is transferred is alkali-developed with a 2% aqueous sodium carbonate solution for 50 seconds, and then rinsed with ultrapure water for 60 seconds. did. This substrate was post-exposed (250 mJ), and the radiation-sensitive resin layer was further cured by post-baking (140 degrees / 25 minutes) to obtain a test piece in which a protective film was formed as a cured film on the substrate.

  In the adhesion test for evaluating the adhesion, a cross-cut guide CCJ-1 manufactured by Cortec Co., Ltd. was used for the substrate on which the protective film was formed. And it evaluated according to the method of the cross cut test (JISK5400-8.5). Specifically, in the evaluation on the ITO substrate, 5B when there is no part peeled off, 4B when part peeled off but 5% or less of the whole peeled off, and the part peeled off exceeds 5% and 15% or less 3B, 2B if the peeled part exceeds 15% and 35% or less, 1B if the peeled part exceeds 35% and 65% or less, and 0B if the peeled part exceeds 65%.

[Evaluation of hardness]
A bar coater (Tester Sangyo AUTO FILM APPLICATOR) was prepared so that the radiation-sensitive resin composition prepared in Examples 1 to 9 was cured on the untreated surface of a polyethylene terephthalate (PET) film as a support film so that the film thickness would be 8 μm after curing. ) And prebaked in a clean oven at 100 ° C./2 minutes to remove the solvent and form a dry film. And the photosensitive dry film in which the radiation sensitive resin layer was formed on the support film was formed.

  Using this photosensitive dry film, the radiation-sensitive resin layer was transferred onto a glass substrate with a laminator (Taisei Laminator FIRST LAMINATOR VAII-700 special type) whose roll temperature was set to 90 ° C., and then a UV exposure machine ( The entire surface was exposed (60 mJ) with a TOPCON Deep-UV exposure machine TME-400PRJ. Next, the PET film of the photosensitive dry film is peeled off, and the substrate on which the radiation-sensitive resin layer of the photosensitive dry film is transferred is alkali-developed with a 2% aqueous sodium carbonate solution for 50 seconds, and then rinsed with ultrapure water for 60 seconds. did. This substrate was post-exposed (250 mJ), and the radiation-sensitive resin layer was further cured by post-baking (140 degrees / 25 minutes) to obtain a test piece in which a protective film was formed as a cured film on the substrate.

  The hardness was measured in accordance with a pencil hardness measurement method (JIS 5600) using a protective film formed on a glass substrate and using a continuous load type scratch strength tester TYPE 18 of Shinto Kagaku Co., Ltd.

[Evaluation of adhesion after pressure cooker test (PCT)]
Using the radiation-sensitive resin compositions prepared in Examples 1 to 9, a test piece formed by forming a protective film on the ITO substrate was prepared in the same manner as the adhesion evaluation described above, and then pressure was applied. A cooker test was conducted, and the adhesion test of the protective film after the pressure cooker was conducted in the same manner as the above-described adhesion evaluation. The pressure cooker used was PC-304R8 manufactured by Hirayama Mfg. Co., Ltd., and the test conditions were 100 ° C / 100% RH / 0.1 MPa for 2 hours (h). And it evaluated by the method similar to evaluation of the adhesiveness mentioned above.

  In Table 1, while showing the composition of the radiation sensitive resin composition prepared in Example 1- Example 9, the evaluation result of the protective film manufactured using them is shown collectively.

As shown in Table 1, the patternability is poor in the protective film having a moisture permeability (water permeability) of about 1000 g / m ² · 24 hours (h) or less when looking at the correlation between patternability, adhesion, and moisture permeability. is there. This is thought to be because the hydrophilicity is low, so the alkali solubility during development is low, and the residue tends to remain.

It can also be seen that when the moisture permeability (water permeability) exceeds about 2000 g / m ² · 24 hours (h), the ITO adhesion after the pressure cooker test (PCT) deteriorates. This is considered to be due to the increase in water absorption of the protective film as the component (D), which mainly contributes to the adhesiveness, increases the water absorption of the protective film, and the protective film swells due to PCT, thereby reducing the adhesiveness. From the above, the protective film is more preferably water permeability after exposure are 1000g ^{/ m} 2 · 24 hours ~2000g ^{/ m} 2 · 24 hours.

  The present invention is not limited to the above embodiments, and various modifications can be made without departing from the spirit of the present invention.

  The touch panel of the present invention has high reliability. Therefore, the touch panel of the present invention is suitable as an input device for portable information equipment that requires excellent display quality and reliability.

21 Touch Panel 22 Transparent Substrate 23 First Detection Electrode 24 Second Detection Electrode 25 Protective Film 28 Intersection 29 Interlayer Insulating Film 30 Electrode Pad 31 Wiring 32 Bridge Wiring 100 Photosensitive Dry Film 101 Support Film 102 Radiation Sensitive Resin Layer 103 Protective Film

Claims (9)

A radiation sensitive resin comprising (A) a binder polymer, (B) a photopolymerization initiator, (C) a compound represented by the following formula (1) and (D) a compound represented by the following formula (2) Composition.
(In the formula (1), X represents an oxygen atom or a sulfur atom, R ¹ and R ² each independently represents a single bond or a divalent to tetravalent organic group, and R ³ and ⁴ each independently represent, Any of an unsaturated heterocyclic group, an alkyl group having 11 to 20 carbon atoms, an oxiranyl group, an oxetanyl group, a vinyl group, a (meth) acryloyloxy group, a hydroxyl group, a carboxyl group, an alkoxysilyl group, a mercapto group, and a sulfo group N and m each independently represent an integer of 1 to 3.)
(In Formula (2), R ¹¹ and R ¹² represent a hydrogen atom or a methyl group. J represents an integer of 1 to 5, and k represents an integer of 1 to 2.) (C) A component is a compound shown by following formula (3), The radiation sensitive resin composition of Claim 1 characterized by the above-mentioned.
(In Formula (3), X represents an oxygen atom or a sulfur atom, R ¹ and R ² each independently represent a single bond or a divalent to tetravalent organic group, and R ⁵ and R ⁶ each independently A hydrogen atom or a methyl group, n and m each independently represent an integer of 1 to 3)   Furthermore, (E) the unsaturated compound which has a urethane bond is included, The radiation sensitive resin composition of Claim 1 or 2 characterized by the above-mentioned.   And (F) inorganic oxide particles that are oxides containing at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, indium, tin, antimony, strontium, barium, cerium, and hafnium. The radiation sensitive resin composition of any one of Claims 1-3 characterized by the above-mentioned.   It forms from the radiation sensitive resin composition of any one of Claims 1-4, The photosensitive dry film characterized by the above-mentioned.   A radiation sensitive resin layer formed with a film thickness of 3 μm to 30 μm on the support film using the radiation sensitive resin composition according to claim 1, and a support film; A photosensitive dry film comprising a protective film disposed on the radiation-sensitive resin layer. Photosensitive dry film according to claim 6 wherein the radiation-sensitive resin layer is cured by exposure, the water permeability after exposure, characterized in that a 1000g ^{/ m} 2 · 24 hours ~2000g ^{/ m} 2 · 24 hours .   The photosensitive dry film according to claim 6, wherein the support film is polyethylene terephthalate. A method for laminating a radiation-sensitive resin layer using the photosensitive dry film according to any one of claims 6 to 8, wherein the radiation-sensitive resin layer is laminated on a sample,
A method for laminating a radiation-sensitive resin layer, wherein the radiation-sensitive resin layer is laminated so that the radiation-sensitive resin layer is in close contact with the sample while removing the protective film.