JP2016071243A - Method for forming resin pattern, method for forming pattern, cured film, liquid crystal display device, organic el display device, and touch panel display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for forming a resin pattern having high sensitivity and resolution and inhibiting generation of a residue, a method for forming a pattern, a cured film obtained from the resin pattern, and a liquid crystal display device, an organic EL display device and a touch panel display device including a pattern or a cured film obtained by the above pattern method.SOLUTION: A method for forming a resin pattern includes in the following order: an application step of applying a specific photosensitive resin composition on a substrate having a reflectance of 20% or more at a wavelength of 313 nm as a step 1; a drying step of forming a photosensitive resin composition layer as a step 2; an exposure step of exposing the layer along a pattern by using specific light radiated from an annular illumination device as a step 3; and a development step of developing the exposed photosensitive resin composition layer as a step 4.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a resin pattern forming method, a pattern forming method, a cured film, a liquid crystal display device, an organic EL display device, and a touch panel display device.

  A TFT (Thin Film Transistor) substrate used for an organic EL display device or a liquid crystal display device which is a flat panel display device has an insulating inorganic transparent film such as SiOx and SiNx, and an oxide transparent conductive film such as ITO and IZO. , Al, Mo, Ti, Cu, W, a metal film made of a laminated film thereof, and a semiconductor film such as Si or an oxide semiconductor are provided in a pattern. For pattern formation of these functional inorganic films, a photosensitive resin composition (etching resist) is applied on each functional inorganic film, solvent removal, pattern exposure and development are performed, and the formed resist pattern is etched as a mask. A method of performing processing is widely known.

  In recent years, high resolution of functional inorganic film processing has been demanded in order to make organic EL display devices and liquid crystal display devices have high-definition display characteristics. In order to finely process a functional inorganic film with high definition, high resolution of a photosensitive resin composition for an etching resist that functions as a mask during etching is required. For this reason, the photosensitive resin composition for etching resists from which a high-definition and fine pattern shape is obtained is examined (for example, patent document 1, patent document 2, etc.).

JP 2009-301007 A JP2013-228675A

In the formation of resin patterns, in recent years, a method of exposing using ultraviolet light having a shorter wavelength has been studied for higher resolution, and exposure using ultraviolet light including i-line (365 nm) and j-line (313 nm) is performed. How to do is known.
Further, as another approach for increasing the resolution, it is known that by using an annular illumination device as a light source, the depth of focus is improved and high illumination exposure is possible.
However, when ultraviolet light containing actinic rays having two or more wavelengths as described above is used for an annular illumination device, and a resin composition formed in a substrate shape with high light reflectance such as a metal substrate is exposed, The incident light and the reflected light interfere with each other to form a standing wave, and the standing waves with the respective wavelengths further interfere with each other, so that a residue is generated in the exposed portion.
A method of forming an antireflection layer on a metal substrate is known in order to prevent the generation of the above-mentioned residue, but there is a problem that productivity is deteriorated because the process of forming the antireflection layer increases. .

  Problems to be solved by the present invention include a method for forming a resin pattern that has high sensitivity and resolution and suppresses generation of a residue, a method for forming a pattern, a cured film obtained from the resin pattern, and a It is to provide a liquid crystal display device, an organic EL display device, and a touch panel display device provided with a pattern or a cured film obtained by the forming method.

The above-described problems of the present invention have been solved by means described in the following <1>, <7>, or <9> to <12>. It is described below together with <2> to <6> or <8> which are preferred embodiments.
<1> As the process 1, the application | coating process which apply | coats the photosensitive resin composition containing the following component A-component C to the board | substrate whose reflectance in 313 nm is 20% or more,
In step 2, the photosensitive resin composition is dried to form a photosensitive resin composition layer, and in step 3, the photosensitive resin composition layer is removed from an annular illumination device using a mercury lamp as a light source. The step of exposing the exposed photosensitive resin composition layer as a step 4 is an exposure step in which a pattern is exposed using light having a j-line ratio expressed by the following formula a of 20% or more. A method of forming a resin pattern, comprising: steps in this order;
Formula a: j-line illuminance / (i-line illuminance + j-line illuminance) × 100 (%)
Component A: Containing a polymer having a structural unit A1 represented by the following formula A1 and / or a polymer having a structural unit A2 represented by the following formula A2, the composition of all polymers for all structural units Polymer component in which the total content of the unit A1 and the structural unit A2 is 15 to 70 mol%. Component B: light having a ratio of absorbance i at 365 nm to absorbance j at 313 nm represented by the following formula b is 50% or less. Acid generator Formula b: i / j × 100 (%)
Component C: Solvent

式Ａ１及び式Ａ２中、Ｒ^A11及びＲ^A12はそれぞれ独立に、水素原子、アルキル基又はアリール基を表し、Ｒ^A11及びＲ^A12の少なくとも一方がアルキル基又はアリール基であり、Ｒ^A13はアルキル基又はアリール基を表し、Ｒ^A11又はＲ^A12と、Ｒ^A13とが連結して環状エーテルを形成してもよく、Ｒ^A11又はＲ^A12と、Ｒ^A13に含まれる炭素数の合計は５以下であり、Ｒ^A14は水素原子又はメチル基を表し、Ｒ^A21及びＲ^A22はそれぞれ独立に、水素原子、アルキル基又はアリール基を表し、少なくともＲ^A21及びＲ^A22のいずれか一方がアルキル基又はアリール基であり、Ｒ^A23はアルキル基又はアリール基を表し、Ｒ^A21又はＲ^A22と、Ｒ^A23とが連結して環状エーテルを形成してもよく、Ｒ^A21又はＲ^A21と、Ｒ^A23に含まれる炭素数の合計は５以下であり、Ｒ^A24は水素原子又はメチル基を表し、Ｘ^A21は単結合又はアリーレン基を表し、＊はそれぞれ独立に、他の構造との結合部位を表す、
＜２＞ 成分Ｂの、式ｂで表される、３１３ｎｍにおける吸光度ｊに対する３６５ｎｍにおける吸光度ｉの割合が１０％以下である、＜１＞に記載の樹脂パターンの形成方法、
＜３＞ 成分Ｂが下記式Ｂ１〜Ｂ４で表される光酸発生剤のうち、少なくとも１つを含む、＜１＞又は＜２＞に記載の樹脂パターンの形成方法、

In Formula A1 and Formula A2, R ^A11 and R ^A12 each independently represent a hydrogen atom, an alkyl group, or an aryl group, at least one of R ^A11 and R ^A12 is an alkyl group or an aryl group, and R ^A13 is an alkyl group Or R ^A11 or R ^A12 and R ^A13 may be linked to form a cyclic ether, and the total number of carbon atoms contained in R ^A11 or R ^A12 and R ^A13 is 5 or less. R ^A14 represents a hydrogen atom or a methyl group, R ^A21 and R ^A22 each independently represents a hydrogen atom, an alkyl group or an aryl group, and at least one of R ^A21 and R ^A22 is an alkyl group or an aryl group R ^A23 represents an alkyl group or an aryl group, and R ^A21 or R ^A22 and R ^A23 may be linked to form a cyclic ether. The number of carbon atoms contained in R ^A21 or R ^A21 and R ^A23 of the total is less than or equal to 5, R ^A24 Represents a hydrogen atom or a methyl group, X ^A21 represents a single bond or an arylene group, * each independently represent a binding site with another structure,
<2> The method of forming a resin pattern according to <1>, wherein the ratio of the absorbance i at 365 nm to the absorbance j at 313 nm represented by formula b of component B is 10% or less,
<3> The method for forming a resin pattern according to <1> or <2>, wherein component B includes at least one of photoacid generators represented by the following formulas B1 to B4.

In Formula B1 to Formula B4, R ^B11 represents an alkyl group having 1 to 10 carbon atoms or an aryl group, and R ^B12 represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 1 to 10 carbon atoms, or a cyano group. R ^{B13 to} R ^B17 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group, and R ^B21 , R ^B22 , and R ^B23 each independently represent 1 to C carbon atoms. 10 represents an alkyl group or an aryl group, at least one of R ^B21 , R ^B22 , and R ^B23 represents an aryl group, X ⁻ represents a monovalent polyatomic anion, and R ^B31 represents a carbon number. Represents an alkyl group or aryl group having 1 to 10; and R ^B41 represents an alkyl group or aryl group having 1 to 10 carbon atoms;
<4> The resin according to any one of <1> to <3>, wherein the exposure step is an exposure step in which exposure is performed using light having a j-line ratio represented by formula a of 50% or more. Pattern formation method,
<5> The method for forming a resin pattern according to any one of <1> to <4>, wherein the substrate is a molybdenum substrate, a titanium substrate, a Cu substrate, a polysilicon substrate, or a silicon nitride substrate.
<6> Component A contains a polymer having the structural unit A1 represented by the formula A1 and / or a polymer having the structural unit A2 represented by the formula A2, and all the structural units of all polymers. The method for forming a resin pattern according to any one of <1> to <5>, wherein the total content of the structural unit A1 and the structural unit A2 is 15 to 60 mol% of a polymer component,
<7> Using the resin pattern formed by the method for forming a resin pattern according to any one of <1> to <6> as a mask, an etching process for etching the substrate, and peeling the formed resin pattern A pattern forming method including, in this order, a peeling step of
<8> The pattern forming method according to <7>, further including a post-baking step of performing a heat treatment after the development step and before the etching step,
<9> A cured film obtained by curing a resin pattern formed by the method for forming a resin pattern according to any one of <1> to <6>,
<10> A liquid crystal display device provided with the pattern formed by the pattern forming method according to <7> or <8>, or the cured film according to <9>,
<11> A pattern formed by the method for forming a pattern according to <7> or <8>, or an organic EL display device provided with the cured film according to <9>,
<12> A touch panel display device comprising the pattern formed by the pattern forming method according to <7> or <8>, or the cured film according to <9>.

  According to the present invention, the resin pattern forming method, the pattern forming method, the cured film obtained from the resin pattern, and the pattern forming method having high sensitivity and resolution and suppressing the generation of residues are obtained. It was possible to provide a liquid crystal display device, an organic EL display device, and a touch panel display device provided with the obtained pattern or cured film.

It is the figure which showed typically an example of the exposure form using a halftone phase difference mask. 1 shows a conceptual diagram of a configuration of an example of an organic EL display device. 1 is a schematic cross-sectional view of a substrate in a bottom emission type organic EL display device. 1 is a conceptual diagram of a configuration of an example of a liquid crystal display device. 1 is a schematic cross-sectional view of an active matrix substrate in a liquid crystal display device.

Hereinafter, the contents of the present invention will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
In the present invention, the description of “lower limit to upper limit” representing a numerical range represents “lower limit or higher and lower limit or lower”, and the description of “upper limit to lower limit” represents “lower limit or higher and lower limit or higher”. That is, it represents a numerical range including an upper limit and a lower limit.
In addition, in the present invention, “the substrate having a reflectance of 20% or higher at 313 nm as Step 1” or the like is simply referred to as “Step 1” or the like. “Component A: The structural unit A1 represented by the following formula A1 is represented by And / or a polymer having a structural unit A2 represented by the following formula A2, and the total content of the structural unit A1 and the structural unit A2 with respect to all the structural units of all the polymers is 15 to 15%. The “polymer component of 70 mol%” or the like is also simply referred to as “component A” or the like.
Furthermore, in the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what does not have a substituent and what has a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In the present invention, “mass%” and “wt%” are synonymous, and “part by mass” and “part by weight” are synonymous.
In the present invention, a combination of two or more preferred embodiments is a more preferred embodiment.

(Method for forming resin pattern)
The method for forming a resin pattern of the present invention includes, as step 1, an application step of applying a photosensitive resin composition containing the following components A to C to a substrate having a reflectance at 313 nm of 20% or more, as step 2. The photosensitive resin composition is dried to form a photosensitive resin composition layer. As step 3, the photosensitive resin composition layer is emitted from an annular illumination device using a mercury lamp as a light source. The exposure process which exposes in pattern form using the light whose j line ratio represented by following formula a is 20% or more, As the process 4, The image development process which develops the said photosensitive resin composition layer exposed. It is characterized by including in this order.
Formula a: j-line illuminance / (i-line illuminance + j-line illuminance) × 100 (%)
Component A: Containing a polymer having a structural unit A1 represented by the following formula A1 and / or a polymer having a structural unit A2 represented by the following formula A2, the composition of all polymers for all structural units Polymer component in which the total content of the unit A1 and the structural unit A2 is 15 to 70 mol%. Component B: light having a ratio of absorbance i at 365 nm to absorbance j at 313 nm represented by the following formula b is 50% or less Acid generator Formula b i / j × 100 (%)
Component C: Solvent

式Ａ１及び式Ａ２中、Ｒ^A11及びＲ^A12はそれぞれ独立に、水素原子、アルキル基又はアリール基を表し、Ｒ^A11及びＲ^A12の少なくとも一方がアルキル基又はアリール基であり、Ｒ^A13はアルキル基又はアリール基を表し、Ｒ^A11又はＲ^A12と、Ｒ^A13とが連結して環状エーテルを形成してもよく、Ｒ^A11又はＲ^A12と、Ｒ^A13に含まれる炭素数の合計は５以下であり、Ｒ^A14は水素原子又はメチル基を表し、Ｒ^A21及びＲ^A22はそれぞれ独立に、水素原子、アルキル基又はアリール基を表し、少なくともＲ^A21及びＲ^A22のいずれか一方がアルキル基又はアリール基であり、Ｒ^A23はアルキル基又はアリール基を表し、Ｒ^A21又はＲ^A22と、Ｒ^A23とが連結して環状エーテルを形成してもよく、Ｒ^A21又はＲ^A21と、Ｒ^A23に含まれる炭素数の合計は５以下であり、Ｒ^A24は水素原子又はメチル基を表し、Ｘ^A21は単結合又はアリーレン基を表し、＊はそれぞれ独立に、他の構造との結合部位を表す。

In Formula A1 and Formula A2, R ^A11 and R ^A12 each independently represent a hydrogen atom, an alkyl group, or an aryl group, at least one of R ^A11 and R ^A12 is an alkyl group or an aryl group, and R ^A13 is an alkyl group Or R ^A11 or R ^A12 and R ^A13 may be linked to form a cyclic ether, and the total number of carbon atoms contained in R ^A11 or R ^A12 and R ^A13 is 5 or less. R ^A14 represents a hydrogen atom or a methyl group, R ^A21 and R ^A22 each independently represents a hydrogen atom, an alkyl group or an aryl group, and at least one of R ^A21 and R ^A22 is an alkyl group or an aryl group R ^A23 represents an alkyl group or an aryl group, and R ^A21 or R ^A22 and R ^A23 may be linked to form a cyclic ether. The number of carbon atoms contained in R ^A21 or R ^A21 and R ^A23 of the total is less than or equal to 5, R ^A24 Represents a hydrogen atom or a methyl group, X ^A21 represents a single bond or an arylene group, * each independently represent a bonding site with the other structures.

  The resin pattern of the present invention is a resin pattern formed by the method for forming a resin pattern of the present invention.

<Application process>
The method for forming a resin pattern of the present invention includes, as step 1, an application step of applying a photosensitive resin composition containing the following components A to C to a substrate having a reflectance of 20% or more at 313 nm.

〔substrate〕
The substrate used in the present invention is a substrate having a reflectance at 313 nm of 20% or more.
The reflectance of the substrate can be selected using a spectrophotometer equipped with an integrating sphere and capable of measuring the total reflectance.
As the substrate used in the method for forming a resin pattern of the present invention, a known substrate can be used without particular limitation as long as the reflectance is within the above range. For example, a chromium substrate, a molybdenum substrate, a titanium substrate, a molybdenum alloy substrate Metal substrates such as tantalum substrate, tantalum alloy substrate, Ni substrate, Cu substrate, Fe substrate, Al substrate; silicon nitride substrate, silicone substrate, silicone nitride substrate, polysilicon substrate, silicone oxide, amorphous silicone film, SOG, semiconductor element Silicone wafers for manufacturing, ceramic materials, single crystal sapphire substrates used for LED lighting, and the like can be used. Among them, in the present invention, a molybdenum substrate, a titanium substrate, a Cu substrate, a polysilicon substrate, or a silicon nitride substrate is preferable, a molybdenum substrate or a silicon substrate is more preferable, and a molybdenum substrate is further preferable. .
The molybdenum substrate or the like is a substrate having a molybdenum layer as a surface layer on the surface of the substrate, and the thickness of the surface layer is preferably 0.05 to 1.0 μm. About the raw material of parts other than a surface layer, it does not specifically limit but a well-known material can be used, For example, glass, quartz, a resin film etc. can be mentioned.
Examples of the resin used for the resin film include polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, polysulfone, polyethersulfone, polyarylate, allyl diglycol carbonate, polyamide, polyimide, polyamideimide, Fluorine resin such as polyetherimide, polybenzoxazole, polybenzazole, polyphenylene sulfide, polycycloolefin, norbornene resin, polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, silicone resin, ionomer resin, cyanate resin, Cross-linked fumaric acid diester resin, cyclic polyolefin, aromatic ether resin, maleimide-olefin tree , Cellulose, episulfide resins.
The shape of the substrate may be a plate shape or a roll shape. Further, the thickness of the inorganic film to be etched is not limited, and may be a film having only a few nm on the surface, or the material of the whole substrate. Moreover, the case where the base-material surface is the composite surface of the said material (board | substrate) may be sufficient.
The substrate is preferably a large substrate of 300 mm × 400 mm or more. In the case of a large-sized substrate, it is important to increase the productivity because a large area of exposure is required. High-illuminance exposure is possible with the annular illumination device using the mercury lamp of the present invention as a light source, and productivity is increased. It is preferable because it is effective for increasing

[Coating method]
As a method for applying the photosensitive resin composition, a known application method can be used without any particular limitation. Methods such as the slit method and the slit and spin method can be used. Furthermore, it is also possible to apply a so-called pre-wet method as described in JP-A-2009-145395.
Although the wet film thickness of the photosensitive resin composition at the time of application | coating is not specifically limited, Usually, it uses in the range of 0.1-10 micrometers.
As the photosensitive resin composition that can be used in the present invention, a photosensitive resin composition containing Component A to Component C can be used.
Preferred embodiments of Component A to Component C will be described later.
Moreover, it is preferable to perform substrate cleaning such as alkali cleaning or plasma cleaning before applying the photosensitive resin resin composition to the substrate.

<Drying process>
The formation method of the metal pattern board | substrate of this invention includes the drying process which dries the said photosensitive resin composition as process 2, and forms the photosensitive resin composition layer.
A drying process is a process of removing the solvent in the photosensitive resin composition.
Although it does not specifically limit as a drying method and it can use a well-known method, It is preferable to dry by pressure reduction (vacuum) and / or heating.
The heating temperature in the drying step is preferably 70 to 130 ° C.
The heating time in the drying step is preferably 30 to 300 seconds.
As a heating method, a known heating method such as a hot plate, an oven, or an infrared heater can be used.
When the temperature and time are within the above ranges, the pattern adhesion is good and the residue can be reduced.
The application process and the drying process may be performed in this order, simultaneously, or alternately. For example, after all the coating in the coating process is completed, the drying process may be performed, or the substrate may be heated and dried while performing the coating process.
Especially, it is preferable to perform a drying process after completion | finish of application | coating in an application | coating process from an adhesive viewpoint.

<Exposure process>
In the method for forming a metal pattern substrate according to the present invention, as step 3, the photosensitive resin composition layer is emitted from an annular illumination device using a mercury lamp as a light source, and the j-line ratio represented by the formula a is 20 The exposure process which exposes in pattern shape using the light which is% or more is included.
In the exposure step, in order to expose the photosensitive resin composition layer in a pattern, it is preferable to irradiate the substrate provided with the photosensitive resin composition layer with actinic rays through a mask having a predetermined pattern.

[Annular illumination device]
In the exposure process of the present invention, an annular illumination device is used.
As the annular illumination device, a known annular illumination device can be used without particular limitation as long as it is a device using a mercury lamp as a light source.
The shape of the aperture stop is not particularly limited as long as it is annular illumination, but 1/2 annular illumination to 2/3 annular illumination is preferably used.
Further, as the light emitted from the annular illumination device, light having a j-line ratio represented by the formula a of 20% or more is used, preferably 50% or more, and more preferably 70% or more. preferable.
In order to achieve the above j-ray ratio, the annular illumination device is preferably a device that can arrange an optical filter such as a short wavelength cut filter or a band pass filter in the optical path.
The spectral filter is not particularly limited as long as it can cut i-line, but quartz glass is preferably used from the viewpoint of transparency.
The j-line ratio is calculated from the above formula a by measuring the illuminance with a UV integrating light meter (UIS-250 (j line), UIT-201 (i line) manufactured by Ushio Electric Co., Ltd.)). can do.
In addition, in order to accelerate the hydrolysis reaction in the region where the acid catalyst is generated, a post-exposure heat treatment (post exposure bake) (hereinafter also referred to as “PEB”) is performed between the exposure step and the development step described later. .)It can be performed. PEB can promote the formation of a carboxyl group or a phenolic hydroxyl group from an acid-decomposable group. The temperature for performing PEB is preferably 30 ° C. or higher and 130 ° C. or lower, more preferably 40 ° C. or higher and 110 ° C. or lower, and particularly preferably 50 ° C. or higher and 100 ° C. or lower.
However, since the acid-decomposable group in the present invention has low activation energy for acid decomposition and is easily decomposed by an acid derived from an acid generator by exposure to generate a carboxyl group or a phenolic hydroxyl group, PEB is not necessarily performed. A positive image can also be formed by development.

When exposure is performed using a mask, a halftone mask can be used in addition to a normal mask.
[Halftone phase difference mask]
The halftone (HT) phase difference mask is a mask that cancels the diffracted light to the peripheral portion of the pattern at the time of exposure with light having an opposite phase. As the halftone (HT) phase difference mask 30, a transparent substrate 32 provided with a phase shifter portion (phase change film 31) having a specific transmittance on the outer periphery of an exposure pattern is used. An exposure form utilizing this is schematically shown in FIG. In FIG. 1, s is a transmission part, k is an exposure part (substrate), 33 is a light intensity distribution, 34 is a light amplitude distribution (positive phase), and 35 is a light amplitude distribution (reverse phase). Yes. As can be seen from this figure, according to this exposure mode, the light whose waveforms are inverted are irradiated adjacent to each other, so that the difference in the amount of light at the edge portion of the pattern is increased and the exposure resolution can be improved. A processing method employing such an exposure method is known, and for example, the procedures and conditions described in JP 2010-8868 A and JP 2007-241136 A can be referred to. The form of the halftone phase difference mask applied to the present invention is not particularly limited. For example, a laminated mask in which the phase shifter layer is divided into a transmittance adjustment layer and a phase adjustment layer may be used.
As described above, a halftone phase difference mask refers to a mask having a transmission part and a phase shifter part. In the present invention, in addition to a mask having a transmission part and a phase shifter part, a transmission part, a phase You may use the mask which has a shifter part and a light-shielding part.

<Development process>
The formation method of the metal pattern board | substrate of this invention includes the image development process which develops the said photosensitive resin composition layer exposed as the process 4. FIG.
In the development step, a copolymer having a liberated carboxyl group or phenolic hydroxyl group is developed using an alkaline developer. A positive image is formed by removing an exposed area containing a resin composition having an acid group that easily dissolves in an alkaline developer, such as a carboxyl group or a phenolic hydroxyl group.
The developer used in the development step preferably contains an aqueous solution of a basic compound. Examples of basic compounds include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkali metal carbonates such as sodium carbonate, potassium carbonate, and cesium carbonate; sodium bicarbonate, potassium bicarbonate Alkali metal bicarbonates such as: tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, diethyldimethylammonium hydroxide, and other tetraalkylammonium hydroxides: Alkyl) trialkylammonium hydroxides; silicates such as sodium silicate and sodium metasilicate; ethylamine, propylamine, diethylamine, triethylammonium Alkylamines such as dimethyl alcohol; alcohol amines such as dimethylethanolamine and triethanolamine; 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5-diazabicyclo- [4.3.0 ] Cycloaliphatic amines such as -5-nonene can be used.
Of these, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide) are preferable.
An aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the alkaline aqueous solution can also be used as a developer.

The pH of the developer is preferably from 9.0 to 15.0, more preferably from 10.0 to 14.0. The concentration of the developer is preferably from 0.1 to 20% by mass, and more preferably from 0.1 to 5.0% by mass.
The development time is preferably 30 to 180 seconds, and the development method may be any of a liquid piling method, a dip method, a shower method, and the like. After the development, washing with running water can be performed for 30 to 300 seconds to form a desired pattern.
A rinsing step can also be performed after development. In the rinsing step, the developed substrate and the development residue are removed by washing the developed substrate with pure water or the like. A known method can be used as the rinsing method. For example, shower rinse and dip rinse can be mentioned.

<Photosensitive resin composition>
Hereinafter, the photosensitive resin composition used in the present invention will be described in detail.
The photosensitive resin composition used in the present invention contains Component A to Component C.
Component A: Containing a polymer having a structural unit A1 represented by the following formula A1 and / or a polymer having a structural unit A2 represented by the following formula A2, the composition of all polymers for all structural units Polymer component in which the total content of the unit A1 and the structural unit A2 is 15 to 70 mol%. Component B: light having a ratio of absorbance i at 365 nm to absorbance j at 313 nm represented by the following formula b is 50% or less. Acid generator Formula b: i / j × 100 (%)
Component C: Solvent

Component A: Containing a polymer having a structural unit A1 represented by the following formula A1 and / or a polymer having a structural unit A2 represented by the following formula A2, the composition of all polymers for all structural units Polymer component whose total content of unit A1 and structural unit A2 is 15-70 mol% Component A in the present invention is structural unit A1 represented by the following formula A1 or structural unit A2 represented by the following formula A2 Containing.
That is, the component A in the present invention contains at least one of the following polymers a1 to a2, and more preferably contains a1 and a2.
Polymer a1: Polymer having a structural unit A1 represented by formula A1 Polymer a2: Polymer having a structural unit A2 represented by formula A2 Component A in the present invention is the above a1 and / or unless otherwise stated In addition to a2, it means one including other polymers added as necessary (for example, polymer a3 described later). In addition, even if it is a high molecular compound, the compound applicable to surfactant mentioned later shall not be contained in the component A.
The total content of the structural unit A1 and the structural unit A2 with respect to all the structural units of all the polymers contained in the component A is 15 to 70 mol%, preferably 15 to 60 mol%, and preferably 15 to 50 mol%. It is more preferable that
Hereinafter, each polymer will be described in detail.

-Polymer a1-
-Structural unit A1- represented by formula A1
The polymer a1 in the present invention is a polymer containing a polymer having the structural unit A1 represented by the formula A1.
When component A contains polymer a1, it can be set as the photosensitive resin composition excellent in resolving power and rectangularity.
In Formula A1, R ^A11 and R ^A12 each independently represent a hydrogen atom, an alkyl group, or an aryl group, and at least one of R ^A11 and R ^A12 is an alkyl group or an aryl group.
As an alkyl group, a C1-C10 alkyl group is preferable, a C1-C8 alkyl group is more preferable, and a C1-C6 alkyl group is still more preferable. The alkyl group may have a substituent. The alkyl group may be linear, branched or cyclic, but is preferably a linear alkyl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a t-butyl group, a pentyl group, a hexyl group, and a cyclohexyl group.
As the aryl group, an aryl group having 6 to 20 carbon atoms is preferable, an aryl group having 6 to 14 carbon atoms is more preferable, and an aryl group having 6 to 10 carbon atoms is still more preferable. The aryl group may have a substituent. Examples of the aryl group include a phenyl group, a naphthyl group, and an anthracenyl group.
Examples of the substituent that the alkyl group and the aryl group may have include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a thioalkoxy group having 1 to 10 carbon atoms, a hydroxyl group, and a cyano group. And halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom) and the like. These substituents may further have a substituent.

Among these, R ^A11 and R ^A12 are preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or a methyl group, one of R ^A11 and R ^A12 is a methyl group, and the other is a hydrogen atom. Particularly preferred is an atom.

R ^A13 represents an alkyl group or an aryl group. The alkyl group and aryl group represented by R ^A13 have the same ^meanings as the alkyl group and aryl group in R ^A11 and R ^A12 . R ^A13 is preferably a methyl group, an ethyl group, or a propyl group, and more preferably an ethyl group or a propyl group.

R ^A13 may be linked to R ^A11 or R ^A12 to form a cyclic ether. The cyclic ether formed by linking with R ^A11 or R ^A12 is preferably a 3- to 6-membered cyclic ether, more preferably a 5- to 6-membered cyclic ether.

  Specific examples of the structural unit A1 include the following structures, but the present invention is not limited to the following structures.

-Structural unit A4-
The polymer a1 preferably contains a polymer having a structural unit A4 represented by the following formula A4 in addition to the structural unit A1, from the viewpoint of high sensitivity.

In Formula A4, R ^A41 is a hydrogen atom or a methyl group, and R ^A41 is preferably a hydrogen atom.
The OH group may be any of p-, m-, and o-, but is preferably bonded to the p-position.

As for the structural unit represented by Formula A4, 50-80 mol% is preferable with respect to all the structural units of the polymer a1, More preferably, it is 60-70 mol%.
If it is the said range, a sensitivity is appropriate and exposure process margin can fully be obtained.

  In the structural unit constituting the polymer a1, the structural unit A1 is preferably 5 to 40 mol%, more preferably 10 to 40 mol%, and even more preferably 20 to 35 mol% with respect to all the structural units of the polymer a1.

  The protection rate of the polymer a1 is preferably 1 to 60%, more preferably 5 to 50%, and still more preferably 10 to 40%. By setting it as such a range, a sensitivity, resolution, and rectangularity will become favorable. A protection rate means the molar ratio of the structural unit which protected the acid by making the sum total of the structural unit which protected the acidic structural unit and the acid in the polymer a1 into 100 mol%.

  The weight average molecular weight (Mw) of the polymer a1 is preferably in the range of 2,000 to 15,000, more preferably 5,000 to 12,000, and still more preferably 7,500 to 12-12. , 000. By setting it to 2,000 or more, an effect that the formed pixel can maintain rectangularity after heating by post-baking is obtained, and by setting it to 15,000 or less, sensitivity and line width stability are improved. Is obtained. Here, the weight average molecular weight is defined by a polystyrene conversion value of gel permeation chromatography.

  The polydispersity (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the polymer a1 is preferably 1.0 to 3.0, more preferably 1.0 to 2.0, and more preferably 1.0 to 2.0. 1.5 is more preferable. By setting it as such a range, the rectangularity of a pixel becomes favorable.

-Polymer a2-
-Structural unit A2- represented by formula A2
The polymer a2 in the present invention is a polymer containing a polymer having the structural unit A2 represented by the formula A2. It can be set as the photosensitive resin composition excellent in a sensitivity because the component A has the polymer a2.

  The polymer component in the composition of the present invention is preferably alkali-insoluble, and is preferably a resin that becomes alkali-soluble when the acid-decomposable group of the structural unit represented by Formula A2 is decomposed. The structural unit having a protected carboxyl group in which the carboxyl group is protected with an acid-decomposable group can generate a carboxyl group by the decomposition of the protective group with an acid. Here, in the present invention, “alkali-soluble” means a coating film (thickness) of the compound (resin) formed by applying a solution of the compound (resin) on a substrate and heating at 90 ° C. for 2 minutes. 3 μm) is a dissolution rate in a 0.4% tetramethylammonium hydroxide aqueous solution at 23 ° C. of 0.01 μm / second or more. “Alkali insoluble” means that the solution of the compound (resin) is a substrate. The dissolution rate of the coating film (thickness 3 μm) of the compound (resin) formed by applying the coating on the substrate and heating at 90 ° C. for 2 minutes in a 0.4% tetramethylammonium hydroxide aqueous solution at 23 ° C. It means less than 0.01 μm / second.

  Examples of the structural unit having a protected carboxyl group protected with an acid-decomposable group include a structural unit having a protected carboxyl group protected with an acid-decomposable group described in paragraphs 0021 to 0055 of JP2012-155288A. Examples of the structural unit having a protected carboxyl group protected with an acid-decomposable group described in paragraphs 0020 to 0052 of Kai 2012-1233091 are shown, the contents of which are incorporated herein. Among them, the polymer a2 is preferably a polymer component having a structural unit A2 having a group in which an acid group having a structure represented by the formula 2A is protected with an acid-decomposable group. The acid group in the present invention means a proton dissociable group having a pKa of less than 7. The acid group is usually incorporated into the polymer as a structural unit containing an acid group using a monomer capable of forming an acid group. By including such a structural unit containing an acid group in the polymer, the polymer tends to be easily dissolved in an alkaline developer. When the component a2 has the structural unit A2, a highly sensitive photosensitive resin composition can be obtained.

In Formula A2, R ^A21 and R ^A22 each independently represent a hydrogen atom, an alkyl group, or an aryl group, at least one of R ^A21 and R ^A22 is an alkyl group or an aryl group, and R ^A23 is an alkyl group or an aryl group R ^A21 or R ^A22 and R ^A23 may be linked to form a cyclic ether, R ^A24 represents a hydrogen atom or a methyl group, and X ^A21 represents a single bond or an arylene group.

When R ^A21 and R ^A22 are alkyl groups, an alkyl group having 1 to 10 carbon atoms is preferable. When R ^A21 and R ^A22 are aryl groups, a phenyl group is preferred. R ^A21 and R ^A22 are each preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
R ^A23 represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms.
X ^A21 represents a single bond or an arylene group, and a single bond is preferred.

  Preferable specific examples of the structural unit represented by Formula A2 include the following structural units. R represents a hydrogen atom or a methyl group.

  10-80 mol% is preferable with respect to all the structural units of the polymer a2, and, as for the structural unit represented by Formula A2, 20-80 mol% is more preferable, and 30-70 mol% is more preferable.

  The protection rate of the polymer a2 is preferably 20 to 100%, more preferably 40 to 90%, and still more preferably 60 to 90%. By setting it as such a range, a sensitivity improves and the difference (discrimination) of the solubility of an exposed part and an unexposed part becomes favorable. A protection rate means the molar ratio of the structural unit which protected the acid by making the sum total of the acidic structural unit and the structural unit which protected the acid in the polymer a2 into 100 mol%.

  The weight average molecular weight (Mw) of the polymer a2 is preferably in the range of 2,000 to 50,000, more preferably 5,000 to 20,000, still more preferably 7,500 to 15 , 000. By setting it to 2,000 or more, it is possible to obtain an effect that the formed pixel can maintain rectangularity even after heating by post-baking, and by setting it to 50,000 or less, it is possible to improve sensitivity and PED characteristics. It is done. Here, the weight average molecular weight is defined by a polystyrene conversion value of gel permeation chromatography.

  The polydispersity (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the polymer a2 is preferably 1.0 to 4.0, more preferably 1.2 to 3.0, and 1.5 to 2.0 is more preferable. By setting it as such a range, the characteristic excellent in the sensitivity and the rectangularity can be acquired.

-Blending ratio of polymer a1 and polymer a2-
It is preferable that the photosensitive resin composition of this invention contains both the polymer a1 and the polymer a2 as a polymer component. These mass ratios are preferably 2: 8 to 8: 2, more preferably 3: 7 to 7: 3, and still more preferably 4: 6 to 6: 4. By setting it as such a range, it exists in the tendency for the effect of this invention to be exhibited more effectively.

-Structural unit A3 and polymer a3-
In the present invention, component A may have other structural unit A3 in addition to the structural units A1, A2 and A4. These structural units may be contained in either one of the polymers a1 and a2 or both. In addition to the polymer a1 or a2, the polymer a3 having another structural unit A3 without substantially including the structural units A1, A2, and A4 may be included. Apart from the polymer a1 or a2, when the polymer a3 having the structural unit A3 without substantially including the structural units A1, A2 and A4 is included, the blending amount of the polymer a3 is based on the total mass of the component A. On the other hand, it is preferably 60% by mass or less, more preferably 40% by mass or less, and further preferably 20% by mass or less.

  There is no restriction | limiting in particular as a structural unit (monomer) used as the other structural unit A3, For example, styrenes, (meth) acrylic acid alkyl ester, (meth) acrylic acid cyclic alkyl ester, (meth) acrylic acid aryl ester, Unsaturated dicarboxylic acid diesters, bicyclounsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated dicarboxylic acid anhydrides, other unsaturated compounds Can be mentioned. Moreover, you may have the structural unit which has an acid group so that it may mention later. Sensitivity can be improved by containing a structural unit having an acid group. As the structural unit having an acid group, acrylic acid, methacrylic acid, and other monomers to be the structural unit A3 can be used alone or in combination of two or more.

In the structural unit constituting the polymer a1, the content of the structural unit A3 is preferably 30 mol% or less, more preferably 20 mol% or less, and still more preferably 10 mol% or less. The lower limit may be 0 mol%, but may be, for example, 1 mol% or more, and further 5 mol% or more. When it is within the above numerical range, various properties of the cured film obtained from the photosensitive resin composition are improved.
In the structural unit constituting the polymer a2, the content of the structural unit A3 is preferably 60 mol% or less, more preferably 50 mol% or less, and still more preferably 40 mol% or less. The lower limit may be 0 mol%, but may be, for example, 1 mol% or more, and further 5 mol% or more. When it is within the above numerical range, various properties of the cured film obtained from the photosensitive resin composition are improved.

In this invention, it is preferable that the structural unit which has an acid group is included as another structural unit (a3). By containing an acid group, it becomes easy to dissolve in an alkaline developer, and the effects of the present invention are more effectively exhibited.
The acid group in the present invention means a proton dissociable group having a pKa of less than 7. The acid group is usually incorporated into the polymer as a structural unit containing an acid group using a monomer capable of forming an acid group. By including such a structural unit containing an acid group in the polymer, the polymer tends to be easily dissolved in an alkaline developer.
Acid groups used in the present invention include those derived from carboxylic acid groups, those derived from sulfonamide groups, those derived from phosphonic acid groups, those derived from sulfonic acid groups, those derived from phenolic hydroxyl groups, sulfones Examples include amide groups, sulfonylimide groups, and the like, and those derived from carboxylic acid groups and / or those derived from phenolic hydroxyl groups are preferred.
The structural unit containing an acid group used in the present invention is more preferably a structural unit derived from styrene, a structural unit derived from a vinyl compound, a structural unit derived from (meth) acrylic acid and / or an ester thereof. .

  In the present invention, it is particularly preferable from the viewpoint of sensitivity to contain a structural unit having a carboxyl group or a structural unit having a phenolic hydroxyl group.

  The structural unit containing an acid group is preferably from 1 to 80 mol%, more preferably from 1 to 50 mol%, still more preferably from 5 to 40 mol%, based on all structural units of the entire polymer.

  As the polymer a3, a resin having a carboxyl group in the side chain is preferable. For example, JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957, JP-A-59-53836, JP-A-59-71048 As described, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc., and side chain Examples thereof include acidic cellulose derivatives having a carboxyl group, those obtained by adding an acid anhydride to a polymer having a hydroxyl group, and high molecular polymers having a (meth) acryloyl group in the side chain.

For example, benzyl (meth) acrylate / (meth) acrylic acid co-A-2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, described in JP-A-7-140654 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid co-A-2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid co-A-2-hydroxyethyl Methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid co-A-2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer It is below.
In addition, JP-A-7-207211, JP-A-8-259876, JP-A-10-300922, JP-A-11-140144, JP-A-11-174224, JP-A-2000-56118 Known polymer compounds described in JP-A-2003-233179, JP-A-2009-52020, and the like can be used, and the contents thereof are incorporated herein.
These polymers may contain only 1 type and may contain 2 or more types.

  As these polymers, commercially available, SMA 1000P, SMA2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P, SMA 3840F (above, manufactured by Sartomer), ARUFON UC-3000, ARUFONUC-3510, ARUFON UC- 3900, ARUFON UC-3910, ARUFON UC-3920, ARUFON UC-3080 (manufactured by Toagosei Co., Ltd.), Joncry 690, Joncryl 678, Joncryl 67, Joncry 586 (manufactured by BASF) and the like can also be used.

  The composition of the present invention preferably contains Component A in a proportion of 60% by mass or more, more preferably 80% by mass or more, based on the total solid content.

Component B: a photoacid generator represented by formula b in which the ratio of absorbance i at 365 nm to absorbance j at 313 nm is 50% or less The photosensitive resin composition used in the present invention is represented by formula b as component B It contains a photoacid generator in which the ratio of absorbance i at 365 nm to absorbance j at 313 nm is 50% or less. The ratio of the absorbance i at 365 nm to the absorbance j at 313 nm is preferably 30% or less, and more preferably 10% or less.
Formula b: i / j × 100 (%)
Also, a photoacid generator that does not satisfy formula b can be used in combination with a sensitizer as long as the mixture of photoacid generator and sensitizer satisfies formula b and generates an acid. Can do. As the photosensitive composition used in the present invention, it is preferable to use only a photoacid generator without combining a sensitizer. The photoacid generator used in the present invention is preferably a photoacid generator that generates an acid having a pKa of 4 or less, more preferably a photoacid generator that generates an acid having a pKa of 3 or less, and an acid of 2 or less. Most preferred are photoacid generators that generate.

Examples of the photoacid generator (B) include onium salt photoacid generators such as iodonium salts and sulfonium salts, sulfonium photoacid generators such as oxime sulfonate and naphthalimide sulfonate, and trihalomethyl photoacids such as trichloromethyltriazine. Examples include generators.
Of these, sulfonium salts, oxime sulfonates, naphthalimide sulfonates, and trichloromethyltriazine structures are preferred.
Moreover, it is preferable that the component B contains at least 1 among the photo-acid generators represented by following formula B1-B4.

In Formula B1 to Formula B4, R ^B11 represents an alkyl group having 1 to 10 carbon atoms or an aryl group, and R ^B12 represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 1 to 10 carbon atoms, or a cyano group. R ^{B13 to} R ^B17 each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group, and R ^B21 , R ^B22 , and R ^B23 each independently represent from 1 carbon atom 10 represents an alkyl group or an aryl group, at least one of R ^B21 , R ^B22 , and R ^B23 represents an aryl group, X ⁻ represents a monovalent polyatomic anion, and R ^B31 represents an alkyl group. Alternatively, it represents an aryl group, and R ^B41 represents an alkyl group having 1 to 10 carbon atoms or an aryl group.

In Formula B1, R ^B11 represents an alkyl group or aryl group having 1 to 10 carbon atoms, preferably an alkyl group or phenyl group having 1 to 6 carbon atoms.
The alkyl group may be substituted with a fluorine atom or the like.
The aryl group may be substituted with an alkyl group or the like.

R ^B12 represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 1 to 10 carbon atoms, or a cyano group, preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group.
The alkyl group may be substituted with an aryl group, a fluorine atom, or the like.
The aryl group may be substituted with an alkyl group or the like.

R ^{B13 to} R ^B17 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group, preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group.
The alkyl group may include an ether bond (—O—) or a thioether bond (—S—).
The aryl group may be substituted with an alkyl group or the like.

In Formula B2, R ^B21 , R ^B22 , and R ^B23 each independently represents an alkyl group having 1 to 10 carbon atoms or an aryl group, and an alkyl group having 1 to 6 carbon atoms, a phenyl group, or a naphthyl group is preferable.
The aryl group may have a substituent Y. Examples of the substituent Y include an alkyl group having 1 to 10 carbon atoms bonded via an oxygen atom or a sulfur atom, an aryl group that may have a substituent Z, a hydroxy group, and a thiol group. Examples of the substituent Z include an alkyl group having 1 to 10 carbon atoms and an acetyl group that may include an ether bond (—O—) or a thioether bond (—S—).
At least one of R ^B21 , R ^B22 , and R ^B23 represents an aryl group.
X ⁻ represents a monovalent polyatomic anion.

In Formula B3, R ^B31 represents an alkyl group or aryl group having 1 to 10 carbon atoms, or represents an aryl group, and an alkyl group or phenyl group having 1 to 6 carbon atoms is preferable.
The alkyl group may be substituted with a fluorine atom or the like.
The aryl group may be substituted with an alkyl group or the like.

In Formula B4, R ^B41 represents an alkyl group having 1 to 10 carbon atoms or an aryl group, preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group.
The aryl group may be substituted with the substituent X. Examples of the substituent X include an alkyl group having 1 to 10 carbon atoms which may include an ether bond (—O—) or a thioether bond (—S—), and a chlorine atom.

  Although the compound of a preferable structure is shown below as component B, it is not limited to this. In the exemplified compounds, Ts represents a tosyl group (p-toluenesulfonyl group), and Me represents a methyl group.

In the photosensitive resin composition of the present invention, the content of Component B is preferably 0.1 to 10% by mass with respect to the total solid mass in the photosensitive resin composition, and is preferably 0.5 to It is more preferable to use 5 parts by mass. Two or more kinds can be used in combination.
In the present invention, other acid generators may be combined.

Component C: Solvent The photosensitive resin composition of the present invention contains a solvent as Component C. The photosensitive resin composition of the present invention is preferably prepared as a solution in which components A and B, which are essential components, and other components described below are dissolved in a solvent. As a solvent used for the preparation of the composition of the present invention, a solvent that uniformly dissolves essential components and optional components and does not react with each component is used.
As the solvent used in the photosensitive resin composition of the present invention, known solvents can be used, such as ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl. Ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether Examples include acetates, esters, ketones, amides, lactones and the like. Moreover, as a specific example of the solvent used for the photosensitive resin composition of this invention, the solvent of paragraph number 0174-0178 of Unexamined-Japanese-Patent No. 2011-221494, paragraph number 0167-0168 of Unexamined-Japanese-Patent No. 2012-194290. And the contents thereof are incorporated herein by reference.

Specific examples of the solvent used in the photosensitive resin composition of the present invention include the solvents described in paragraphs 0174 to 0178 of JP2011-221494A.
In addition, benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonal as necessary for these solvents. , Benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate, propylene carbonate and the like can also be added. These solvents can be used alone or in combination of two or more. The solvent that can be used in the present invention is a single type or a combination of two types, more preferably a combination of two types, propylene glycol monoalkyl ether acetates or dialkyl ethers, diacetates. And diethylene glycol dialkyl ethers or esters and butylene glycol alkyl ether acetates are more preferably used in combination.

Component C is preferably a solvent having a boiling point of 130 ° C. or more and less than 160 ° C., a solvent having a boiling point of 160 ° C. or more, or a mixture thereof, a solvent having a boiling point of 130 ° C. or more and less than 160 ° C., a boiling point of 160 ° C. or more and 200 ° C. A solvent having a boiling point of 130 ° C. or lower or a mixture thereof is more preferable, and a solvent having a boiling point of 130 ° C. or higher and lower than 160 ° C. and a solvent having a boiling point of 160 ° C. or higher and 200 ° C. or lower is still more preferable.
Solvents having a boiling point of 130 ° C. or higher and lower than 160 ° C. include propylene glycol monomethyl ether acetate (boiling point 146 ° C.), propylene glycol monoethyl ether acetate (boiling point 158 ° C.), propylene glycol methyl-n-butyl ether (boiling point 155 ° C.), propylene glycol An example is methyl-n-propyl ether (boiling point 131 ° C.).
Solvents having a boiling point of 160 ° C. or higher include ethyl 3-ethoxypropionate (boiling point 170 ° C.), diethylene glycol methyl ethyl ether (boiling point 176 ° C.), propylene glycol monomethyl ether propionate (boiling point 160 ° C.), dipropylene glycol methyl ether acetate. (Boiling point 213 ° C), 3-methoxybutyl ether acetate (boiling point 171 ° C), diethylene glycol diethyl ether (boiling point 189 ° C), diethylene glycol dimethyl ether (boiling point 162 ° C), propylene glycol diacetate (boiling point 190 ° C), diethylene glycol monoethyl ether acetate (Boiling point 220 ° C), dipropylene glycol dimethyl ether (boiling point 175 ° C), 1,3-butylene glycol diacetate (boiling point 232 ° C) It can be.

  The content of Component C in the photosensitive resin composition of the present invention is preferably 50 to 3,000 parts by mass, and 100 to 2,000 parts per 100 parts by mass of the total resin components in the photosensitive resin composition. It is more preferable that it is a mass part, and it is still more preferable that it is 150-1,500 mass parts.

<Other ingredients>
In addition to Component A, Component B, and Component C, the positive photosensitive resin composition of the present invention includes, as necessary, a compound having a crosslinkable group as Component D, a basic compound as Component E, As the component F, a basic compound, as the component G, an antioxidant, and as the component H, a sensitizer can be preferably added. Further, the photosensitive resin composition of the present invention includes an acid proliferation agent, a development accelerator, a plasticizer, a thermal radical generator, a thermal acid generator, an ultraviolet absorber, a thickener, and an organic or inorganic precipitation inhibitor. Known additives such as can be added. Examples of the other components include compounds described in paragraphs 0180 and 0228 of JP2011-221494A.

Component D: Compound having a crosslinkable group The photosensitive resin composition is a component D having a molecular weight of 100 to 2,000 having a crosslinkable group (hereinafter also referred to as “crosslinking agent”) as necessary. It is preferable to contain. By adding a crosslinking agent, the cured film obtained from the photosensitive resin composition can be made stronger.
The crosslinking agent is not limited as long as it causes a crosslinking reaction by heat (except for component A). That is, a thermal crosslinking agent is preferably used as the crosslinking agent. For example, a compound having two or more epoxy groups or oxetanyl groups in the molecule described below, an alkoxymethyl group-containing crosslinking agent, a compound having at least one ethylenically unsaturated bond, a blocked isocyanate compound, or an alkoxysilane compound Etc. can be added. Especially, the compound which has 2 or more epoxy groups or oxetanyl groups in a molecule | numerator is preferable, and the compound which has 2 or more epoxy groups in a molecule | numerator is more preferable.
Further it, as the crosslinkable group in the crosslinking agent, an epoxy group, oxetanyl ^{_{group, -NH-CH 2 -OR E1,}} ( meth) acryloyl group, and at least one selected from the group consisting of blocked isocyanate groups Is preferred. R ^E1 represents an alkyl group having 1 to 20 carbon atoms.

The addition amount of the crosslinking agent in the photosensitive resin composition is preferably 0 to 50 parts by mass and more preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the solid content of the photosensitive resin composition. Preferably, it is 0.5-10 mass parts. By adding in this range, a cured film excellent in mechanical strength and solvent resistance can be obtained. A plurality of crosslinking agents may be used in combination. In that case, the content is calculated by adding all the crosslinking agents.
The molecular weight of Component D is preferably 100 to 2,000, preferably 100 to 1,500, and more preferably 100 to 1,000.

<Compound having two or more epoxy groups or oxetanyl groups in the molecule>
Specific examples of compounds having two or more epoxy groups in the molecule include bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, aliphatic epoxy resins, and the like. Can do.

These are available as commercial products. For example, JER152, JER157S70, JER157S65, JER806, JER828, JER1007 (manufactured by Mitsubishi Chemical Holdings Co., Ltd.) and the like are listed in JP01-221494A, paragraph 0189, etc. In addition, ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4011S (manufactured by ADEKA), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN- 502 (above, manufactured by ADEKA Corporation), Denacol EX-611, EX-612, EX-614, EX-614B, EX-622, EX-512, EX-521, EX-411, EX-421, EX- 313, EX-314, EX- 21, EX-211, EX-212, EX-810, EX-811, EX-850, EX-851, EX-821, EX-830, EX-832, EX-841, EX-911, EX-941, EX-920, EX-931, EX-212L, EX-214L, EX-216L, EX-321L, EX-850L, DLC-201, DLC-203, DLC-204, DLC-205, DLC-206, DLC- 301, DLC-402 (above, manufactured by Nagase ChemteX Corporation), YH-300, YH-301, YH-302, YH-315, YH-324, YH-325 (above, Nippon Steel Chemical Co., Ltd.) Manufactured), Celoxide 2021P, Celoxide 2081 (manufactured by Daicel Corporation), and the like.
These can be used alone or in combination of two or more.

  Among these, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin and aliphatic epoxy resin are more preferable, and bisphenol A type epoxy resin is particularly preferable.

As specific examples of the compound having two or more oxetanyl groups in the molecule, Aron oxetane OXT-121, OXT-221, OX-SQ, and PNOX (manufactured by Toagosei Co., Ltd.) can be used.
Moreover, it is preferable to use the compound containing an oxetanyl group individually or in mixture with the compound containing an epoxy group.

<Alkoxymethyl group-containing crosslinking agent>
As the alkoxymethyl group-containing crosslinking agent, alkoxymethylated melamine, alkoxymethylated benzoguanamine, alkoxymethylated glycoluril, alkoxymethylated urea and the like are preferable. These can be obtained by converting the methylol group of methylolated melamine, methylolated benzoguanamine, methylolated glycoluril, or methylolated urea to an alkoxymethyl group, respectively. The type of the alkoxymethyl group is not particularly limited, and examples thereof include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, and a butoxymethyl group. From the viewpoint of outgas generation amount, A methyl group is particularly preferred.
Further, as the alkoxymethyl group, -NH-CH ₂ -OR ¹ are preferably exemplified. R ¹ represents an alkyl group having 1 to 20 carbon atoms.
Among these crosslinkable compounds, alkoxymethylated melamine, alkoxymethylated benzoguanamine, and alkoxymethylated glycoluril are mentioned as preferable crosslinkable compounds, and alkoxymethylated glycoluril is particularly preferable from the viewpoint of transparency.
These alkoxymethyl group-containing crosslinking agents are available as commercial products. For example, Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156, 1158, 1123, 1170, 1174, UFR65, 300 (above, manufactured by Mitsui Cyanamid Co., Ltd.), Nicarax MX-750, -032, -706, -708, -40, -31, -270, -280, -290, Nicarac MS-11, Nicarak MW-30HM, -100LM, -390, (manufactured by Sanwa Chemical Co., Ltd.) and the like can be preferably used.

<Block isocyanate compound>
In the photosensitive resin composition, a blocked isocyanate compound can also be preferably employed as a crosslinking agent. The blocked isocyanate compound is not particularly limited as long as it is a compound having a blocked isocyanate group, but is preferably a compound having two or more blocked isocyanate groups in one molecule from the viewpoint of curability.
In addition, the blocked isocyanate group in this invention is a group which can produce | generate an isocyanate group with a heat | fever, For example, the group which reacted the blocking agent and the isocyanate group and protected the isocyanate group can illustrate preferably. Moreover, it is preferable that the said blocked isocyanate group is a group which can produce | generate an isocyanate group with the heat | fever of 90 to 250 degreeC.
Further, the skeleton of the blocked isocyanate compound is not particularly limited and may be any as long as it has two isocyanate groups in one molecule, and is aliphatic, alicyclic or aromatic. Polyisocyanate may be used, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 1,3-trimethylene diisocyanate, 1,4-tetramethylene Diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,9-nonamethylene diisocyanate, 1,10-decamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 2, '-Diethyl ether diisocyanate, diphenylmethane-4,4'-diisocyanate, o-xylene diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, methylene bis (cyclohexyl isocyanate), cyclohexane-1,3-dimethylene diisocyanate, cyclohexane-1, 4-dimethylene diisocyanate, 1,5-naphthalene diisocyanate, p-phenylene diisocyanate, 3,3′-methylene ditolylene-4,4′-diisocyanate, 4,4′-diphenyl ether diisocyanate, tetrachlorophenylene diisocyanate, norbornane diisocyanate, Isocyanate compounds such as hydrogenated 1,3-xylylene diisocyanate and hydrogenated 1,4-xylylene diisocyanate And prepolymer-type skeleton compounds derived from these compounds can be suitably used. Among these, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), and isophorone diisocyanate (IPDI) are particularly preferable.

Examples of the mother structure of the blocked isocyanate compound in the photosensitive resin composition include biuret type, isocyanurate type, adduct type, and bifunctional prepolymer type.
Examples of the blocking agent that forms the block structure of the blocked isocyanate compound include oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, and imide compounds. be able to. Among these, a blocking agent selected from oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, and pyrazole compounds is particularly preferable.

Examples of the oxime compound include aldoxime and ketoxime, and specific examples include acetoxime, formaldoxime, cyclohexane oxime, methyl ethyl ketone oxime, cyclohexanone oxime, and benzophenone oxime.
Examples of the lactam compound include ε-caprolactam and γ-butyrolactam.
Examples of the phenol compound include phenol, naphthol, cresol, xylenol, and halogen-substituted phenol.
Examples of the alcohol compound include methanol, ethanol, propanol, butanol, cyclohexanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, and alkyl lactate.
As said amine compound, a primary amine and a secondary amine are mentioned, Any of an aromatic amine, an aliphatic amine, and an alicyclic amine may be sufficient, An aniline, a diphenylamine, ethyleneimine, a polyethyleneimine etc. can be illustrated.
Examples of the active methylene compound include diethyl malonate, dimethyl malonate, ethyl acetoacetate, methyl acetoacetate and the like.
Examples of the pyrazole compound include pyrazole, methylpyrazole, dimethylpyrazole and the like.
Examples of the mercaptan compound include alkyl mercaptans and aryl mercaptans.

  The blocked isocyanate compound that can be used in the photosensitive resin composition is available as a commercial product. For example, Coronate AP Stable M, Coronate 2503, 2515, 2507, 2513, 2555, Millionate MS-50 (above, Nippon Polyurethane Industry) Takenate B-830, B-815N, B-820NSU, B-842N, B-84N, B-870N, B-874N, B-882N (Mitsui Chemicals, Inc.), Duranate 17B-60PX, 17B-60P, TPA-B80X, TPA-B80E, MF-B60X, MF-B60B, MF-K60X, MF-K60B, E402-B80B, SBN-70D, SBB-70P, K6000 (above, Asahi Kasei Chemicals) Manufactured by Co., Ltd.), Death Module BL1100 Preferably, BL1265 MPA / X, BL3575 / 1, BL3272MPA, BL3370MPA, BL3475BA / SN, BL5375MPA, VPLS2078 / 2, BL4265SN, PL340, PL350, Sumidur BL3175 (above, manufactured by Sumika Bayer Urethane Co., Ltd.) Can do.

<Alkoxysilane compound>
The photosensitive resin composition may contain an alkoxysilane compound as a crosslinking agent. Preferred examples of the alkoxysilane compound include trialkoxysilane compounds.
Examples of the alkoxysilane compound include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltriacoxysilane, γ-glycidoxypropylalkyldialkoxysilane, and γ-methacryloxy. Propyltrialkoxysilane, γ-methacryloxypropylalkyldialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrialkoxysilane, vinyltrialkoxysilane Is mentioned. Of these, γ-glycidoxypropyltrialkoxysilane and γ-methacryloxypropyltrialkoxysilane are more preferable, γ-glycidoxypropyltrialkoxysilane is more preferable, and 3-glycidoxypropyltrimethoxysilane is particularly preferable. preferable. These can be used alone or in combination of two or more.

Moreover, the compound represented by the following formula can also be preferably employed.
(R ^D11 ) _4-n- Si- (OR ² ) _n
In the formula, R ^D11 is a hydrocarbon group having 1 to 20 carbon atoms having no reactive group, R ² is an alkyl group having 1 to 3 carbon atoms or a phenyl group, and n is an integer of 1 to 3. is there.
Specific examples include the following compounds. Ph represents a phenyl group.

The alkoxysilane compound in the photosensitive resin composition is not particularly limited, and a known one can be used.
Moreover, when an alkoxysilane compound is used, in addition to the effect of improving the surface hardness, the adhesion between the film formed of the photosensitive resin composition and the substrate can be improved.

<Compound having at least one ethylenically unsaturated bond>
As the compound having at least one ethylenically unsaturated bond, a (meth) acrylate compound such as a monofunctional (meth) acrylate, a bifunctional (meth) acrylate, a trifunctional or higher (meth) acrylate, or the like is preferably used. it can.
Examples of the monofunctional (meth) acrylate include 2-hydroxyethyl (meth) acrylate, carbitol (meth) acrylate, isobornyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, and 2- (meth) acryloyloxyethyl. And 2-hydroxypropyl phthalate.
Examples of the bifunctional (meth) acrylate include ethylene glycol (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate, Examples include tetraethylene glycol di (meth) acrylate, bisphenoxyethanol full orange acrylate, and bisphenoxyethanol full orange acrylate.
Examples of the trifunctional or higher functional (meth) acrylate include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri ((meth) acryloyloxyethyl) phosphate, pentaerythritol tetra (meth) acrylate, Examples include dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate.
These compounds having at least one ethylenically unsaturated bond are used singly or in combination of two or more.
Moreover, when adding the compound which has at least 1 ethylenically unsaturated bond, it is preferable to add a radical polymerization initiator and it is more preferable to add a thermal radical polymerization initiator. Known radical polymerization initiators can be used.
Moreover, if it is a compound which has a (meth) acryl group, the bridge | crosslinking by Michael addition reaction is also possible.

Component E: Basic Compound The photosensitive resin composition may contain a basic compound as Component E.
Component E can be arbitrarily selected from those used in chemically amplified resists. Examples include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, quaternary ammonium salts of carboxylic acids, and the like. Specific examples thereof include compounds described in paragraphs 0204 to 0207 of JP2011-221494A.

Specific examples of the aliphatic amine include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine, and the like. Examples include ethanolamine, dicyclohexylamine, and dicyclohexylmethylamine.
Examples of the aromatic amine include aniline, benzylamine, N, N-dimethylaniline, diphenylamine and the like.
Examples of the heterocyclic amine include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinamide, quinoline, 8-oxyquinoline, pyrazine, Pyrazole, pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, N-cyclohexyl-N ′-[2- (4-morpholinyl) ethyl] thiourea, 1,5-diazabicyclo [4.3.0 ] -5-Nonene, 1,8-di And azabicyclo [5.3.0] -7-undecene.
Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, and tetra-n-hexylammonium hydroxide.
Examples of the quaternary ammonium salt of carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, and tetra-n-butylammonium benzoate.
Among these, heterocyclic amines are preferable, and 2,4,5-triphenylimidazole and / or N-cyclohexyl-N ′-[2- (4-morpholinyl) ethyl] thiourea is particularly preferable.

The basic compounds that can be used in the present invention may be used singly or in combination of two or more.
It is preferable that content of the basic compound in the photosensitive resin composition is 0.001-5 mass parts with respect to 100 mass parts of solid content in the photosensitive resin composition, and is 0.005-3 mass parts. More preferably.

Component F: Surfactant The photosensitive resin composition may contain a surfactant as Component F.
Component F can be any of anionic, cationic, nonionic or amphoteric, but a preferred surfactant is a nonionic surfactant. Examples of the surfactant used in the photosensitive resin composition include those described in paragraphs 0201 to 0205 of JP2012-88459A and those described in paragraphs 0185 to 0188 of JP2011-215580A. And these descriptions are incorporated herein.
Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone-based and fluorine-based surfactants. . The following trade names are KP-341, X-22-822 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 99C (manufactured by Kyoeisha Chemical Co., Ltd.), F Top (manufactured by Mitsubishi Materials Denka Kasei Co., Ltd.), Mega Fuck (manufactured by DIC Corporation), Florard Novec FC-4430 (manufactured by Sumitomo 3M Co., Ltd.), Surflon Each series such as S-242 (manufactured by AGC Seimi Chemical Co., Ltd.), PolyFox PF-6320 (manufactured by OMNOVA), SH-8400 (manufactured by Toray Dow Corning Silicone Co., Ltd.), and footgent FTX-218G (manufactured by Neos) Can be mentioned.
Moreover, the weight average of polystyrene conversion measured by the gel permeation chromatography when tetrahydrofuran (THF) is used as a surfactant contains the structural unit A and the structural unit B represented by the following formula G-1. A preferable example is a copolymer having a molecular weight (Mw) of 1,000 or more and 10,000 or less.

式（Ｇ−１）中、Ｒ⁴⁰¹及びＲ⁴⁰³はそれぞれ独立に、水素原子又はメチル基を表し、Ｒ⁴⁰²は炭素数１以上４以下の直鎖アルキレン基を表し、Ｒ⁴⁰⁴は水素原子又は炭素数１以上４以下のアルキル基を表し、Ｌは炭素数３以上６以下のアルキレン基を表し、ｐ及びｑは重合比を表す質量百分率であり、ｐは１０質量％以上８０質量％以下の数値を表し、ｑは２０質量％以上９０質量％以下の数値を表し、ｒは１以上１８以下の整数を表し、ｓは１以上１０以下の整数を表す。

In formula (G-1), R ⁴⁰¹ and R ⁴⁰³ each independently represent a hydrogen atom or a methyl group, R ⁴⁰² represents a linear alkylene group having 1 to 4 carbon atoms, and R ⁴⁰⁴ represents a hydrogen atom or carbon. Represents an alkyl group having 1 to 4 carbon atoms, L represents an alkylene group having 3 to 6 carbon atoms, p and q are mass percentages representing a polymerization ratio, and p is a numerical value of 10 mass% to 80 mass%. Q represents a numerical value of 20% to 90% by mass, r represents an integer of 1 to 18, and s represents an integer of 1 to 10.

The L is preferably a branched alkylene group represented by the following formula G-2. R ⁴⁰⁵ in Formula G-2 represents an alkyl group having 1 to 4 carbon atoms, and is preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability with respect to the coated surface. More preferred is an alkyl group of 3. The sum (p + q) of p and q is preferably p + q = 100, that is, 100% by mass.

  The weight average molecular weight (Mw) of the copolymer is more preferably from 1,500 to 5,000.

These surfactants can be used individually by 1 type or in mixture of 2 or more types.
The addition amount of the surfactant in the photosensitive resin composition is preferably 10 parts by mass or less, more preferably 0.001 to 10 parts by mass with respect to 100 parts by mass of the solid content in the photosensitive resin composition. Preferably, it is 0.01-3 mass parts.

Component G: Antioxidant It is preferable that the photosensitive resin composition contains an antioxidant. As an antioxidant, a well-known antioxidant can be contained. By adding an antioxidant, there is an advantage that coloring of the cured film can be prevented, or a decrease in film thickness due to decomposition can be reduced, and heat resistant transparency is excellent.
Examples of such antioxidants include phosphorus antioxidants, amides, hydrazides, hindered amine antioxidants, sulfur antioxidants, phenol antioxidants, ascorbic acids, zinc sulfate, sugars, Examples thereof include nitrates, sulfites, thiosulfates, and hydroxylamine derivatives. Of these, phenol-based antioxidants, amide-based antioxidants, hydrazide-based antioxidants, and sulfur-based antioxidants are particularly preferable from the viewpoint of coloring the cured film and reducing film thickness, with phenol-based antioxidants being the most preferred. preferable. These may be used individually by 1 type and may mix 2 or more types.
Specific examples include the compounds described in paragraphs 0026 to 0031 of JP-A-2005-29515, the contents of which are incorporated herein.

  Examples of commercially available phenolic antioxidants include ADK STAB AO-15, ADK STAB AO-18, ADK STAB AO-20, ADK STAB AO-23, ADK STAB AO-30, ADK STAB AO-37, ADK STAB AO-40 and ADK STAB AO. -50, ADK STAB AO-51, ADK STAB AO-60, ADK STAB AO-70, ADK STAB AO-80, ADK STAB AO-330, ADK STAB AO-412S, ADK STAB AO-503, ADK STAB A-611, ADK STAB A-612, ADK STAB A -613, ADK STAB PEP-4C, ADK STAB PEP-8, ADK STAB PEP-8W, ADK STAB PEP-24G, ADK STAB PEP-36, ADK STAB PEP-36Z, ADK STAB HP-1 , ADK STAB 2112, ADK STAB 260, ADK STAB 1522, ADK STAB 1178, ADK STAB 1500, ADK STAB 135A, ADK STAB 3010, ADK STAB TPP, ADK STAB CDA-1, ADK STAB CDA-6, ADK STAB ZS-27, ADK STAB ZS 90, ADK STAB ZS 90 -91 (above, manufactured by ADEKA Corporation), Irganox 245FF, Irganox 1010FF, Irganox 1010, Irganox MD1024, Irganox 1035FF, Irganox 1035, Irganox 1098, Irganox 1330, Irganox 1520L, Irganox 3114, Irganox 1726, Irgafos 168, Irgamod 295 (BAS Company, Ltd.), Tinuvin 405 (manufactured by BASF), and the like. Among them, ADK STAB AO-60, ADK STAB AO-80, Irganox 1726, Irganox 1035, Irganox 1098, and Tinuvin 405 can be preferably used.

The content of the antioxidant is preferably 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, based on 100 parts by mass of the solid content of the photosensitive resin composition. It is particularly preferably 5 to 4% by mass. By setting it within this range, sufficient transparency of the formed film can be obtained, and the sensitivity at the time of pattern formation can be improved.
Further, as additives other than antioxidants, various ultraviolet absorbers described in “New Development of Polymer Additives” (Nikkan Kogyo Shimbun Co., Ltd.), metal deactivators, and the like are used in the present invention. You may add to a resin composition.

Component H: Sensitizer The photosensitive resin composition preferably contains a sensitizer in combination with Component B in order to promote its decomposition. The sensitizer absorbs actinic rays or radiation and enters an electronically excited state. The sensitizer in an electronically excited state comes into contact with the photoacid generator, and effects such as electron transfer, energy transfer, and heat generation occur. As a result, the photoacid generator undergoes a chemical change and decomposes to generate an acid. Examples of preferred sensitizers include compounds belonging to the following compounds and having an absorption wavelength in any of the wavelength ranges from 350 nm to 450 nm.

Polynuclear aromatics (eg, pyrene, perylene, triphenylene, anthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 3,7-dimethoxyanthracene, 9,10-dipropyloxyanthracene), xanthenes (For example, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), xanthones (for example, xanthone, thioxanthone, dimethylthioxanthone, diethylthioxanthone), cyanines (for example, thiacarbocyanine, oxacarbocyanine), merocyanines (Eg, merocyanine, carbomerocyanine), rhodocyanins, oxonols, thiazines (eg, thionine, methylene blue, toluidine blue), acridines (eg, acridineo , Chloroflavin, acriflavine), acridones (eg, acridone, 10-butyl-2-chloroacridone), anthraquinones (eg, anthraquinone), squariums (eg, squalium), styryls, base styryls ( For example, 2- {2- [4- (dimethylamino) phenyl] ethenyl} benzoxazole), coumarins (eg, 7-diethylamino-4-methylcoumarin, 7-hydroxy-4-methylcoumarin, 2, 3, 6 , 7-tetrahydro-9-methyl-1H, 5H, 11H [1] benzopyrano [6,7,8-ij] quinolidine-11-non).
Among these sensitizers, polynuclear aromatics, acridones, styryls, base styryls, and coumarins are preferable, and polynuclear aromatics are more preferable. Of the polynuclear aromatics, anthracene derivatives are most preferred.

The addition amount of the sensitizer in the photosensitive resin composition is preferably 0 to 1,000 parts by mass, and 10 to 500 parts by mass with respect to 100 parts by mass of the photoacid generator of the photosensitive resin composition. More preferably, it is more preferably 50 to 200 parts by mass.
Moreover, a sensitizer may be used individually by 1 type and can also use 2 or more types together.

[Other ingredients]
In the photosensitive resin composition, in addition to the above components, an ultraviolet absorber, a metal deactivator, an acid multiplier, a development accelerator, a plasticizer, a thermal radical generator, and a thermal acid generator are added as necessary. , Known additives such as thickeners and organic or inorganic suspending agents can be added. Moreover, as these compounds, the description of paragraph 0201-0224 of Unexamined-Japanese-Patent No. 2012-88459 can also be considered, for example, The content of these is integrated in this-application specification.

-Acid multiplier-
The photosensitive resin composition may use an acid proliferating agent for the purpose of improving sensitivity.
The acid proliferating agent that can be used in the present invention is a compound that can further generate an acid by an acid-catalyzed reaction to increase the acid concentration in the reaction system, and is a compound that exists stably in the absence of an acid. is there.
Specific examples of such an acid proliferating agent include the acid proliferating agents described in paragraphs 0226 to 0228 of JP2011-221494A, the contents of which are incorporated herein.

  The content of the acid multiplication agent in the photosensitive resin composition is 10 to 1,000 parts by mass with respect to 100 parts by mass of the photoacid generator, in view of the dissolution contrast between the exposed part and the unexposed part. To 20 to 500 parts by mass.

-Development accelerator-
The photosensitive resin composition can contain a development accelerator.
As the development accelerator, any compound having a development acceleration effect can be used, and the development accelerator may be a compound having at least one structure selected from the group consisting of a carboxy group, a phenolic hydroxyl group, and an alkyleneoxy group. Preferably, a compound having a carboxy group or a phenolic hydroxyl group is more preferable, and a compound having a phenolic hydroxyl group is most preferable.
As the development accelerator, the description in paragraphs 0171 to 0172 of JP2012-042837A can be referred to, and the contents thereof are incorporated in the present specification.

A development accelerator may be used individually by 1 type, and can also use 2 or more types together.
The addition amount of the development accelerator in the photosensitive resin composition is preferably 0 to 30 parts by mass, preferably 0.1 to 20 parts per 100 parts by mass of the solid content of the photosensitive resin composition, from the viewpoints of sensitivity and residual film ratio. A mass part is more preferable, and it is most preferable that it is 0.5-10 mass parts.
The molecular weight of the development accelerator is preferably from 100 to 2,000, more preferably from 150 to 1,500, still more preferably from 150 to 1,000.

-Plasticizer-
The photosensitive resin composition may contain a plasticizer.
Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, didodecyl phthalate, polyethylene glycol, glycerin, dimethyl glycerin phthalate, dibutyl tartrate, dioctyl adipate, and triacetyl glycerin.
The plasticizer content in the photosensitive resin composition is preferably 0.1 to 30 parts by mass, and more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the component A content.

  Further, as other additives, a thermal radical generator described in paragraphs 0120 to 0121 of JP2012-8223A, and a nitrogen-containing compound and a thermal acid generator described in International Publication No. 2011-136704 are also used. The contents of which are incorporated herein by reference.

[Method for preparing photosensitive resin composition]
The photosensitive resin composition can be prepared by mixing each component in a predetermined ratio and in an arbitrary method, stirring and dissolving the photosensitive resin composition. For example, a resin composition can be prepared by preparing a solution in which the components are previously dissolved in a solvent and then mixing them in a predetermined ratio. The composition solution prepared as described above can be used after being filtered using, for example, a filter having a pore size of 0.2 μm.

(Pattern and formation method thereof)
The pattern forming method of the present invention includes an etching process for etching the substrate and a peeling process for peeling the formed resin pattern, using the resin pattern formed by the resin pattern forming method of the present invention as a mask. It is characterized by including in order.
The pattern of the present invention is a pattern formed by the pattern forming method of the present invention.

<Etching process>
The pattern forming method of the present invention includes an etching step of etching the substrate using the resin pattern formed by the resin pattern forming method of the present invention as a mask.
There is no restriction | limiting in particular as an etching method in an etching process, A well-known etching method can be used.
The etching in the etching step may be wet etching or dry etching, but from the viewpoint of cost, wet etching is preferable.
Moreover, there is no restriction | limiting in particular also about etching conditions, It can carry out by arbitrary temperature, time, and atmosphere.
There is no restriction | limiting in particular as an etching liquid used for wet etching, A well-known etching liquid can be used, What is necessary is just to select suitably according to the material of the metal film to be used, and the material of a resist. For example, the etching liquid composition described in Unexamined-Japanese-Patent No. 2013-89731 or Unexamined-Japanese-Patent No. 2011-228618 is mentioned suitably. Specific examples include an aqueous iron chloride solution and hydrofluoric acid.

<Peeling process>
The pattern forming method of the present invention includes a peeling step for peeling the formed resin pattern.
There is no restriction | limiting in particular as a method of peeling the said resin pattern, A well-known method can be used. Further, the resist pattern may be removed by plasma treatment or chemical treatment.

<Post-bake process>
The pattern forming method of the present invention preferably further includes a post-bake step of performing a heat treatment after the development step and before the etching step.
According to the post-baking step, for example, when the photosensitive resin composition layer includes a group that can be used for a crosslinking reaction such as an acid group and an epoxy group, by heating the photosensitive resin composition layer after development, A cured film can be formed.
This heating is performed using a heating device such as a hot plate or an oven at a predetermined temperature, for example, 90 ° C. to 200 ° C. for a predetermined time, for example, 3 to 30 minutes on the hot plate, 5 to 30 minutes for the oven. It is preferable to process.

(Cured film)
The cured film of the present invention is a cured film formed by curing a resin pattern formed by the resin pattern forming method of the present invention.
The resin pattern is cured at a predetermined temperature, for example, 100 to 250 ° C., using a heating device such as a hot plate or an oven for a pattern corresponding to an unexposed area obtained by development after the development step. It is preferable to form by heat treatment for a time, for example, 5 to 60 minutes on a hot plate, and 30 to 90 minutes for an oven.
Moreover, when performing heat processing, transparency of a cured film can also be improved by performing in nitrogen atmosphere.
Prior to the heat treatment, the substrate on which the cured film is formed in a pattern can be re-exposed with actinic rays and then heated.

The exposure in the re-exposure step may be performed by the same means as in the exposure step. However, in the re-exposure step, the entire surface of the substrate on the side where the film is formed by the photosensitive resin composition of the present invention is used. It is preferable to perform exposure. A preferable exposure amount for the re-exposure step is 100 to 1,000 mJ / cm ² .

(Organic EL display device)
The organic EL display device of the present invention includes a pattern formed by the pattern forming method of the present invention or a cured film of the present invention.
The organic EL display device of the present invention is not particularly limited, and examples thereof include various known organic EL display devices and liquid crystal display devices having various structures.
For example, specific examples of TFT (Thin-Film Transistor) included in the organic EL display device of the present invention include amorphous silicon-TFT, low-temperature polysilicon-TFT, oxide semiconductor TFT, and the like. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.
FIG. 2 is a conceptual diagram of an example of an organic EL display device. 1 is a schematic cross-sectional view of a substrate in a bottom emission type organic EL display device.
A bottom gate type TFT 1 is formed on a glass substrate 6, and an insulating film 3 made of Si ₃ N ₄ is formed so as to cover the TFT 1. A contact hole (not shown) is formed in the insulating film 3, and then a wiring 2 (height: 1.0 μm) connected to the TFT 1 through the contact hole is formed on the insulating film 3. The wiring 2 is used to connect the TFT 1 with an organic EL element formed between the TFTs 1 or in a later process.
Further, in order to flatten the unevenness due to the formation of the wiring 2, a planarizing layer 4 is formed on the insulating film 3 in a state where the unevenness due to the wiring 2 is embedded.
On the planarizing film 4, a bottom emission type organic EL element is formed. That is, the first electrode 5 made of ITO is formed on the planarizing film 4 so as to be connected to the wiring 2 through the contact hole 7. The first electrode 5 corresponds to the anode of the organic EL element.
An insulating film 8 having a shape covering the periphery of the first electrode 5 is formed. By providing the insulating film 8, a short circuit between the first electrode 5 and the second electrode formed in the subsequent process is prevented. can do.
Further, although not shown in FIG. 2, a hole transport layer, an organic light emitting layer, and an electron transport layer are sequentially deposited through a desired pattern mask, and then a second layer made of Al is formed on the entire surface above the substrate. An active matrix organic material in which two electrodes are formed and sealed by bonding using a sealing glass plate and an ultraviolet curable epoxy resin, and each organic EL element is connected to a TFT 1 for driving it. An EL display device is obtained.

(Liquid crystal display device)
The liquid crystal display device of the present invention comprises a pattern formed by the pattern forming method of the present invention or a cured film of the present invention.
The liquid crystal display device of the present invention is not particularly limited, and examples thereof include known liquid crystal display devices having various structures.
For example, specific examples of TFT (Thin-Film Transistor) included in the liquid crystal display device of the present invention include amorphous silicon-TFT, low-temperature polysilicon-TFT, oxide semiconductor TFT, and the like. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.
In addition, as a liquid crystal driving method that can be taken by the liquid crystal display device of the present invention, a TN (Twisted Nematic) method, a VA (Virtual Alignment) method, an IPS (In-Place-Switching) method, an FFS (Frings Field Switching) method, an OCB (Optical) method. Compensated Bend) method and the like.
In the panel configuration, the cured film of the present invention can also be used in a COA (Color Filter on Array) type liquid crystal display device. For example, the organic insulating film (115) of JP-A-2005-284291, or JP-A-2005 -346054 can be used as the organic insulating film (212).
Specific examples of the alignment method of the liquid crystal alignment film that the liquid crystal display device of the present invention can take include a rubbing alignment method and a photo alignment method. Further, the polymer orientation may be supported by a PSA (Polymer Sustained Alignment) technique described in JP-A Nos. 2003-149647 and 2011-257734.
Moreover, the cured film of this invention is not limited to the said use, It can be used for various uses. For example, in addition to the planarization film and interlayer insulating film, a protective film for the color filter, a spacer for keeping the thickness of the liquid crystal layer in the liquid crystal display device constant, a microlens provided on the color filter in the solid-state imaging device, etc. Can be suitably used.
FIG. 3 is a conceptual cross-sectional view showing an example of the active matrix type liquid crystal display device 10. The color liquid crystal display device 10 is a liquid crystal panel having a backlight unit 12 on the back surface, and the liquid crystal panel includes all pixels disposed between two glass substrates 14 and 15 having a polarizing film attached thereto. The elements of the TFT 16 corresponding to are arranged. Each element formed on the glass substrate is wired with an ITO transparent electrode 19 that forms a pixel electrode through a contact hole 18 formed in the cured film 17. On the ITO transparent electrode 19, an RGB color filter 22 in which a liquid crystal 20 layer and a black matrix are arranged is provided.
The light source of the backlight is not particularly limited, and a known light source can be used. For example, a white LED, a multicolor LED such as blue, red, and green, a fluorescent lamp (cold cathode tube), and an organic EL can be used.
Further, the liquid crystal display device can be a 3D (stereoscopic) type or a touch panel type. It is also possible to make it flexible.

  Since the photosensitive resin composition of the present invention has good pixel rectangularity, a resist pattern formed using the photosensitive resin composition of the present invention is used as a partition wall of a MEMS device. Examples of such MEMS devices include parts such as SAW filters, BAW filters, gyro sensors, display micro shutters, image sensors, electronic paper, inkjet heads, biochips, sealants, and the like. More specific examples are exemplified in JP-T-2007-522531, JP-A-2008-250200, JP-A-2009-263544, and the like.

(Touch panel, touch panel display device, and manufacturing method thereof)
The touch panel of the present invention includes a pattern formed by the pattern forming method of the present invention or a cured film of the present invention.
The touch panel display device of the present invention has at least a display function and includes a pattern formed by the pattern forming method of the present invention.
The touch panel formation method of the present invention includes the pattern formation method of the present invention.
Moreover, the manufacturing method of the touchscreen display device of this invention includes the formation method of the pattern of this invention.

The touch panel of the present invention can be more suitably used as a capacitive touch panel.
In addition, the touch panel of the present invention and the touch panel display device of the present invention are not particularly limited. The configuration described in the publication can be referred to.
The touch panel of the present invention or the touch panel display device of the present invention is the latest touch panel technology (published July 6, 2009, Techno Times), supervised by Yuji Mitani, “Touch Panel Technology and Development”, Co., Ltd. The configurations disclosed in CM Publishing (2004, 12), FPD International 2009 Forum T-11 Lecture Textbook, Cypress Semiconductor Corporation Application Note AN2292, etc. can be applied.
The touch panel type may be an external type or a display integrated type. A film sensor can be mentioned as an external type.
Examples of the display-integrated type include a so-called on-cell type (for example, FIG. 19 in JP 2013-168125 A) and other configurations (for example, FIG. 6 in JP 2013-164871 A).

  Although the usage form of the touch panel of this invention is not specifically limited, It is suitable to set it as a combined touch panel display device with an organic EL display device or a liquid crystal display device.

  The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

In the following synthesis examples, the following symbols represent the following compounds, respectively.
MAEVE: 1-ethoxyethyl methacrylate MATHF: tetrahydro-2H-furan-2-yl methacrylate PHS: parahydroxystyrene BzMA: (benzyl methacrylate) (manufactured by Wako Pure Chemical Industries, Ltd.)
MMA: Methyl methacrylate MAA: Methacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.)
HEMA: Hydroxyethyl methacrylate (Wako Pure Chemical Industries, Ltd.)
PGMEA: Propylene glycol monomethyl ether acetate V-65: 2,2′-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.)
V-601: Dimethyl-2,2′-azobis (2-methylpropionate) (manufactured by Wako Pure Chemical Industries, Ltd.)
HMDS: Hexamethyldisilane

(Synthesis Example 1: Synthesis of A1-1)
20 g of an alkali-soluble resin (VP-8000 manufactured by Nippon Soda Co., Ltd.) and 320 g of propylene glycol monomethyl ether acetate (PGMEA) were dissolved in a flask, distilled under reduced pressure, and water and PGMEA were distilled off azeotropically. After confirming that the water content was sufficiently low, 24 g of ethyl vinyl ether and 0.35 g of p-toluenesulfonic acid were added and stirred at room temperature for 1 hour. Thereto, 0.28 g of triethylamine was added to stop the reaction. After adding ethyl acetate to the reaction solution and further washing with water, ethyl acetate, water and azeotropic PGMEA were distilled off by distillation under reduced pressure to obtain A1-1 which is an alkali-soluble resin protected with an acid-decomposable group. It was. The weight average molecular weight of the obtained resin was 20,000. The polydispersity was 1.13.
The structure of A1-1 is a 1-ethoxyethyl protector of p-hydroxystyrene / p-hydroxystyrene copolymer (30 mol% / 70 mol%).

(Synthesis Example 2: Synthesis of A1-2)
15.6 g of alkali-soluble resin (VP-8000 manufactured by Nippon Soda Co., Ltd.) and 100 g of propylene glycol monomethyl ether acetate (PGMEA) were dissolved in a flask and distilled under reduced pressure, and water and PGMEA were distilled off azeotropically. After confirming that the water content was sufficiently low, 2.7 g of 2,3-dihydrofuran and 0.015 g of p-toluenesulfonic acid were added and stirred at room temperature for 2 hours. Thereto was added 0.090 g of triethylamine to stop the reaction. Ethyl acetate was added to the reaction solution, and the mixture was further washed with water. Then, ethyl acetate and water were distilled off under reduced pressure to obtain A1-2 which is a soluble resin having a protection rate of 25 mol%. The weight average molecular weight of the obtained resin was 12,000. The polydispersity was 1.13.
The structure of A1-2 is a 2-tetrahydrofuranyl protector / p-hydroxystyrene copolymer of p-hydroxystyrene (30 mol% / 70 mol%).

(Synthesis Example 3: Synthesis of A1-3)
A1-3 was synthesized in the same manner as in Synthesis Example 3 except that the amount of 2,3-dihydrofuran was changed to 6.3 g. The structure of A1-2 is a 2-tetrahydrofuranyl protector of p-hydroxystyrene / p-hydroxystyrene copolymer (70 mol% / 30 mol%).

(A1-4)
The following polymers described in JP2009-301007 were used.

(Synthesis Example 4: Synthesis of A2-1)
A2-1 which is a copolymer was synthesized as follows.
To 144.2 parts (2 molar equivalents) of ethyl vinyl ether, 0.5 part of phenothiazine was added, and 86.1 parts (1 molar equivalent) of methacrylic acid was added dropwise while cooling the reaction system to 10 ° C. or lower. ) For 4 hours. After adding 5.0 parts of pyridinium p-toluenesulfonate, the mixture was stirred at room temperature for 2 hours and allowed to stand overnight at room temperature. To the reaction solution, 5 parts of sodium bicarbonate and 5 parts of sodium sulfate were added, and the mixture was stirred at room temperature for 1 hour. Insoluble matter was filtered and concentrated under reduced pressure at 40 ° C. or lower, and the yellow oily residue was distilled under reduced pressure to obtain a boiling point (bp .) 134.0 parts of 1-ethoxyethyl methacrylate (MAEVE) fraction of 43-45 ° C./7 mmHg was obtained as a colorless oil.
1-ethoxyethyl methacrylate (63.28 parts (0.4 molar equivalent)), BzMA (52.83 parts (0.3 molar equivalent)), MAA (8.61 parts (0.1 molar equivalent) )), HEMA (26.03 parts (0.2 molar equivalent)) and PGMEA (110.8 parts) were heated to 70 ° C. under a nitrogen stream. While stirring this mixed solution, a mixed solution of radical polymerization initiator V-65 (trade name, manufactured by Wako Pure Chemical Industries, Ltd., 4 parts) and PGMEA (100.0 parts) was added dropwise over 2.5 hours. did. After completion of the dropping, the reaction was carried out at 70 ° C. for 4 hours to obtain an EDM solution of polymer (solid content concentration: 40%).
The weight average molecular weight measured by gel permeation chromatography (GPC) of the obtained A2-1 was 15,000.

(Synthesis of MATHF)
Methacrylic acid (86 g, 1 mol) was cooled to 15 ° C., and camphorsulfonic acid (4.6 g, 0.02 mol) was added. To the solution, 2-dihydrofuran (71 g, 1 mol, 1.0 equivalent) was added dropwise. After stirring for 1 hour, saturated sodium bicarbonate (500 mL) was added, extracted with ethyl acetate (500 mL), dried over magnesium sulfate, insolubles were filtered and concentrated under reduced pressure at 40 ° C. or lower to give a residual yellow oily product. Distillation under reduced pressure afforded 125 g of tetrahydro-2H-furan-2-yl methacrylate (MATHF) as a colorless oily substance (yield 80%) at a boiling point (bp.) Of 54 to 56 ° C./3.5 mmHg.

<Synthesis of other polymers>
Other copolymers were synthesized in the same manner as the synthesis of the polymer A2-1 except that the monomers used and the amounts used were changed to those shown in the following table. In the table, the unit is a molar ratio.

(Preparation of photosensitive resin composition)
The following components A and B and components D to F described below are dissolved and mixed in a solvent (PGMEA) so that the solid content concentration is 12% by mass, and the filter is made of polytetrafluoroethylene having a diameter of 0.2 μm. And the photosensitive resin compositions of Examples and Comparative Examples were obtained. The amount of each component used was as follows. The compounding ratio of component A is as shown in the following table, and symbols such as B-2 described in the type column of component B in the table correspond to exemplary compound B-2 described in the description of component B above. ing. B-18 and B-19 are compounds having the following structures. Ingredients with “-” in the table mean that they are not contained in the composition.

(Examples 1-8, Examples 11-22, and Comparative Examples 1-9)
Component A (solid content excluding solvent) 96.8% by mass relative to the total solid content
Component B 3.0% by mass relative to the total solid content
Component E 0.1% by mass with respect to the total solid content
Component F 0.1% by mass with respect to the total solid content
Example 9
The same procedure as in Example 2 was performed except that the amount of component B added was 1.5 mass% with respect to the total solid content, and the amount of component A added was 98.3 mass% with respect to the total solid content.
(Example 10)
The same procedure as in Example 2 was performed except that the addition amount of component B was 6.0% by mass with respect to the total solid content, and the addition amount of component A was 93.8% by mass with respect to the total solid content.

The detail of each component used in the Example is as follows.
B-1: PAI-101 manufactured by Midori Chemical Co., Ltd.
B-2: synthesized according to the method described in paragraph 0108 of JP-T-2002-528451.
・ B-3: PAG203 manufactured by BASF
・ B-4: CGI1906 manufactured by BASF
・ B-5: CGI1907 manufactured by BASF
-B-6: B7 mixture: Cyracure UVI-6976 made by BASF
-B-8: GSID-26-1 manufactured by BASF
・ B-9: NDS-105 manufactured by Midori Chemical Co., Ltd.
・ B-10: NDS-103 manufactured by Midori Chemical Co., Ltd.
-B-11: Midori Chemical Co., Ltd. NMPS-109
・ B-12: NAI-105 manufactured by Midori Chemical Co., Ltd.
-B-13: NAI-100 manufactured by Midori Chemical Co., Ltd.
・ B-14: NAI-101 manufactured by Midori Chemical Co., Ltd.
-B-15: TAZ-102 manufactured by Midori Chemical Co., Ltd.
・ B-16: TAZ-103 manufactured by Midori Chemical Co., Ltd.
・ B-17: TAZ-104 manufactured by Midori Chemical Co., Ltd.
-B-18: PAG103 manufactured by BASF
・ B-19: TAZ-204 manufactured by Midori Chemical Co., Ltd.
E-1: (Manufacturer: Toyo Kasei Kogyo Co., Ltd., product number: CMTU)
F-1: (compound with the following structure, synthetic product)

(Evaluation)
<Sensitivity>
A photosensitive resin composition having a film thickness of 1.3 μm was applied to each of the substrates shown in Table 2 that had been washed and treated with HMDS (hexamethyldisilazane) and had a reflectance at 313 nm of 20% or more, and a mask. The light emitted from the annular illumination device using a mercury lamp as a light source via the light is exposed using light whose illuminance ratio (j-line ratio) of j-line and i-line is adjusted using an optical filter, and is 2.38. % Of the resin pattern obtained by paddle development with 100% tetramethylammonium hydroxide (TMAH) for 60 seconds and rinsed with pure water. The sensitivity was evaluated as The exposure amount was calculated using a j-ray illuminometer manufactured by Ushio Co., Ltd. based on the j-ray exposure amount. 3 or more is a practically acceptable level, 4 or more is preferable, and 5 is more preferable.
1: An exposure amount of 100 mJ / cm ² or more is required 2: An exposure amount of 50 mJ / cm ² or more and less than 100 mJ / cm ² is required 3: An exposure amount of 20 mJ / cm ² or more and less than 50 mJ / cm ² is required 4:10 mJ / An exposure dose of cm ² or more and less than 20 mJ / cm ² is required 5: An exposure dose of less than 10 mJ / cm ²

<Evaluation of resolution>
An annular illumination device using a mercury lamp as a light source through a mask by applying a photosensitive resin composition with a film thickness of 1.3 μm to a substrate described in Table 2 that has been cleaned and treated with HMDS (hexamethyldisilazane) The light emitted from the light is exposed using a light whose ratio of j-line and i-line is adjusted using an optical filter, and paddle development is performed for 60 seconds using 2.38% tetramethylammonium hydroxide (TMAH). The smallest pattern that can be resolved with a 1: 1 line-and-space pattern of the resin pattern obtained by rinsing with pure water was defined as the resolution. 3 or more is a practically acceptable level, 4 or more is preferable, and 5 is more preferable.
1: Resolution of 3 μm or more 2: 2.5 μm is resolved, but 2.0 μm is not resolved 3: 2.0 μm is resolved, but 1.7 μm is not resolved 4: 1.7 μm is resolved 1.5 μm does not resolve 5: 1.5 μm resolves

<Residue>
An annular illumination device using a mercury lamp as a light source through a mask by applying a photosensitive resin composition with a film thickness of 1.3 μm to a substrate described in Table 2 that has been cleaned and treated with HMDS (hexamethyldisilazane) The light emitted from the light is exposed using a light whose ratio of j-line and i-line is adjusted using an optical filter, and paddle development is performed for 60 seconds using 2.38% tetramethylammonium hydroxide (TMAH). SEM image of 3um line and space pattern of resin pattern obtained by rinsing with pure water. Residues near the line pattern were evaluated. 3 or more is a practically acceptable level, 4 or more is preferable, and 5 is more preferable.
1: The width of the residue is 0.5 μm or more on one side 2: The width of the residue is 0.2 μm or more and less than 0.5 μm on one side 3: The width of the residue is 0.1 μm or more and less than 0.2 μm on one side 4: The width of the residue is 0. 05 μm or more and less than 0.1 μm 5: No residue is generated

  1: TFT (thin film transistor), 2: wiring, 3: insulating film, 4: planarization film, 5: first electrode, 6: glass substrate, 7: contact hole, 8: insulating film, 10: liquid crystal display device, 12: Backlight unit, 14, 15: Glass substrate, 16: TFT, 17: Cured film, 18: Contact hole, 19: ITO transparent electrode, 20: Liquid crystal, 22: Color filter, 30: Halftone phase difference mask, 31: Phase shifter part (phase change film), 32: Transparent base material, 33, 34, 35: Exposure intensity curve, s: Transmission part, k: Exposure part (substrate), 33: Light intensity distribution, 34: Light amplitude Distribution (positive phase), 35: Light amplitude distribution (reverse phase)

Claims (12)

As a process 1, an application process of applying a photosensitive resin composition containing the following components A to C to a substrate having a reflectance at 313 nm of 20% or more,
Step 2 is a drying step of drying the photosensitive resin composition to form a photosensitive resin composition layer.
In step 3, the photosensitive resin composition layer is patterned from light emitted from a ring illumination device using a mercury lamp as a light source and having a j-line ratio represented by the following formula a of 20% or more. Exposure process for exposing to,
A process for forming a resin pattern comprising, as step 4, a developing step of developing the exposed photosensitive resin composition layer in this order.
Formula a: j-line illuminance / (i-line illuminance + j-line illuminance) × 100 (%)
Component A: Containing a polymer having a structural unit A1 represented by the following formula A1 and / or a polymer having a structural unit A2 represented by the following formula A2, the composition of all polymers for all structural units Polymer component in which the total content of the unit A1 and the structural unit A2 is 15 to 70 mol%. Component B: light having a ratio of absorbance i at 365 nm to absorbance j at 313 nm represented by the following formula b is 50% or less. Acid generator Formula b: i / j × 100 (%)
Component C: Solvent

In Formula A1 and Formula A2, R ^A11 and R ^A12 each independently represent a hydrogen atom, an alkyl group, or an aryl group, at least one of R ^A11 and R ^A12 is an alkyl group or an aryl group, and R ^A13 is an alkyl group Or R ^A11 or R ^A12 and R ^A13 may be linked to form a cyclic ether, and the total number of carbon atoms contained in R ^A11 or R ^A12 and R ^A13 is 5 or less. R ^A14 represents a hydrogen atom or a methyl group, R ^A21 and R ^A22 each independently represents a hydrogen atom, an alkyl group or an aryl group, and at least one of R ^A21 and R ^A22 is an alkyl group or an aryl group R ^A23 represents an alkyl group or an aryl group, and R ^A21 or R ^A22 and R ^A23 may be linked to form a cyclic ether. The number of carbon atoms contained in R ^A21 or R ^A21 and R ^A23 of the total is less than or equal to 5, R ^A24 Represents a hydrogen atom or a methyl group, X ^A21 represents a single bond or an arylene group, * each independently represent a bonding site with the other structures.   The method for forming a resin pattern according to claim 1, wherein the ratio of the absorbance i at 365 nm to the absorbance j at 313 nm represented by formula b of component B is 10% or less. The formation method of the resin pattern of Claim 1 or 2 in which the component B contains at least 1 among the photo-acid generators represented by following formula B1-B4.

In Formula B1 to Formula B4, R ^B11 represents an alkyl group having 1 to 10 carbon atoms or an aryl group, and R ^B12 represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 1 to 10 carbon atoms, or a cyano group. R ^{B13 to} R ^B17 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group, and R ^B21 , R ^B22 , and R ^B23 each independently represent 1 to C carbon atoms. 10 represents an alkyl group or an aryl group, at least one of R ^B21 , R ^B22 , and R ^B23 represents an aryl group, X ⁻ represents a monovalent polyatomic anion, and R ^B31 represents a carbon number. R 1 represents a C 1-10 alkyl group or aryl group, and R ^B41 represents a C 1-10 alkyl group or aryl group.   The method for forming a resin pattern according to any one of claims 1 to 3, wherein the exposure step is an exposure step in which exposure is performed using light having a j-line ratio represented by formula a of 50% or more.   The method for forming a resin pattern according to claim 1, wherein the substrate is a molybdenum substrate, a titanium substrate, a Cu substrate, a polysilicon substrate, or a silicon nitride substrate.   Component A contains a polymer having the structural unit A1 represented by the formula A1 and / or a polymer having the structural unit A2 represented by the formula A2, and is a structural unit for all the structural units of all polymers. The method for forming a resin pattern according to any one of claims 1 to 5, wherein the total content of A1 and the structural unit A2 is a polymer component of 15 to 60 mol%. An etching step of etching the substrate using the resin pattern formed by the method for forming a resin pattern according to claim 1 as a mask, and
Including a peeling step of peeling the formed resin pattern in this order,
Pattern formation method.   The pattern forming method according to claim 7, further comprising a post-bake step of performing a heat treatment after the development step and before the etching step.   The cured film formed by hardening the resin pattern formed by the formation method of the resin pattern of any one of Claims 1-6.   A liquid crystal display device comprising the pattern formed by the pattern forming method according to claim 7 or 8, or the cured film according to claim 9.   An organic EL display device comprising the pattern formed by the pattern forming method according to claim 7 or 8, or the cured film according to claim 9.   A touch panel display comprising the pattern formed by the pattern forming method according to claim 7 or 8, or the cured film according to claim 9.

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