JP2012189875A - Resin pattern, manufacturing method for the same, manufacturing method for mems structure, manufacturing method for semiconductor element, and manufacturing method for plating pattern - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method for a resin pattern, that can manufacture a rectangular or substantially rectangular resin pattern even after performing thermal treatment on a formed resin pattern.SOLUTION: The manufacturing method for a resin pattern includes at least the following steps (1) to (6) in this order: (1) an application step of applying a photosensitive resin composition on a substrate; (2) a solvent removal step of removing solvent from the applied photosensitive resin composition; (3) an exposure step of exposing the photosensitive resin composition, from which the solvent has been removed, with an active light beam to form a pattern; (4) a development step of developing the exposed photosensitive resin composition with an aqueous developing solution; (5) a plasma treatment step of performing plasma treatment by having a surface of the developed photosensitive resin composition in contact with ions and/or radicals generated from the gas made into plasma; and (6) a thermal treatment step of performing thermal treatment on the photosensitive resin composition which has been subjected to the plasma treatment.

Description

  The present invention relates to a resin pattern and a manufacturing method thereof, a manufacturing method of a MEMS structure, a manufacturing method of a semiconductor element, and a plating pattern manufacturing method.

In a manufacturing process of a liquid crystal display device, an organic EL display device, a semiconductor device, a MEMS, or the like, a photosensitive resin composition is used as a structure or an etching resist.
As a conventional photosensitive resin composition, for example, Patent Document 1 proposes a positive photosensitive resin composition for an etching resist.
Patent Document 2 shows an example of manufacturing a MEMS structure using a sacrificial layer resist.

Japanese Patent Laid-Open No. 10-73923 Special table 2008-533510 gazette

For example, resist shape control is important during MEMS fabrication.
In addition, when used as an etching resist in a dry etching process, a rectangular profile with a large taper angle is required to produce a precise pattern by etching.

In the conventional photosensitive resin composition, when heat treatment (baking) for improving the cured film strength is performed, it is difficult to obtain a rectangle or a profile close to a rectangle.
For example, the photosensitive resin composition described in Patent Document 1 has a problem that a rectangular profile cannot be obtained due to the heat flow during baking.
The problem to be solved by the present invention is to provide a resin pattern manufacturing method capable of manufacturing a rectangular or near-rectangular resin pattern even after heat treatment of the formed resin pattern.

The above-described problems of the present invention have been solved by means described in the following <1> or <16> to <20>. It is described below together with <2> to <15> which are preferred embodiments.
<1> A resin pattern manufacturing method comprising at least steps (1) to (6) in this order,
(1) Application process for applying photosensitive resin composition on substrate (2) Solvent removal process for removing solvent from applied photosensitive resin composition (3) Activated photosensitive resin composition from which solvent has been removed (4) Development step of developing the exposed photosensitive resin composition with an aqueous developer (5) Ions generated from the surface of the developed photosensitive resin composition and plasmaized gas And / or a plasma treatment step in which a radical is brought into contact with the plasma treatment (6) a heat treatment step of heat treating the plasma-treated photosensitive resin composition <2> between step (4) and step (5), or The resin pattern manufacturing method as described in said <1> including the post-exposure process exposed between a process (5) and a process (6),
<3> The method for producing a resin pattern according to <1> or <2>, wherein the cross-sectional taper angle of the resin pattern is 70 ° or more after the heat treatment step of the step (6),
<4> The resin pattern manufacturing method according to any one of the above <1> to <3>, wherein the film thickness of the resin pattern is 4 to 100 μm after the heat treatment step of the step (6),
<5> The resin pattern manufacturing method according to any one of <1> to <4>, wherein the gas is a gas not containing oxygen,
<6> The resin pattern manufacturing method according to any one of <1> to <5>, wherein the gas is a gas containing a fluorine compound.
<7> The photosensitive resin composition comprises (component A1) (a1-1) a monomer unit having a residue in which a carboxy group or a phenolic hydroxyl group is protected with an acid-decomposable group, and (a1-2) an epoxy group. And / or a polymer having a monomer unit having an oxetanyl group, (Component B1) a photoacid generator, and (Component C1) a solvent, according to any one of the above <1> to <6> Resin pattern manufacturing method,
<8> The method for producing a resin pattern according to <7>, wherein the photosensitive resin composition further includes (Component D1) a thermal crosslinking agent,
<9> Component D1 contains the block isocyanate compound, The resin pattern manufacturing method as described in said <8>,
<10> Any of the above <7> to <9>, wherein the component A1 further includes a monomer unit having a ring structure (a1-3) in addition to the monomer units (a1-1) and (a1-2) The resin pattern manufacturing method as described in one,

<11> In the above <7> to <10>, the component A1 further includes (a1-4) a monomer unit having a carboxy group or a hydroxyl group in addition to the monomer units (a1-1) and (a1-2). The resin pattern manufacturing method according to any one of the above,
<12> The content of the monomer unit (a1-1) in the component A is 45 mol% or less with respect to all the monomer units of the component A, according to any one of the above <7> to <11>. Resin pattern manufacturing method,
<13> The method for producing a resin pattern according to any one of the above <1> to <12>, wherein the photosensitive resin composition is a chemically amplified positive photosensitive resin composition,
<14> The photosensitive resin composition comprises (Component A2) (a2-1) a monomer unit having a carboxy group or a phenolic hydroxyl group, and (a2-2) a monomer unit having an epoxy group and / or an oxetanyl group. A resin pattern production method according to any one of the above <1> to <6>, comprising a polymer having, (Component B2) a quinonediazide compound, and (Component C2) a solvent;
<15> The photosensitive resin composition comprises (Component A3) a polymer having a carboxy group or a phenolic hydroxyl group, (Component B3) a photopolymerization initiator, (Component C3) a solvent, and (Component D3) a polymerizable monomer. A resin pattern production method according to any one of the above <1> to <6>,
<16> A resin pattern produced by the resin pattern production method according to any one of <1> to <15> above,
<17> A MEMS structure manufacturing method for manufacturing a structure using the resin pattern according to the above <16> as a sacrificial layer at the time of stacking the structure,
<18> A method for producing a MEMS structure using the resin pattern according to <16> as a member of the MEMS structure,
<19> A method for manufacturing a semiconductor element, which uses the resin pattern described in <16> as an etching resist to produce a pattern on a substrate,
<20> A plating pattern manufacturing method for manufacturing by plating using the resin pattern according to the above <16> as a mold.

  ADVANTAGE OF THE INVENTION According to this invention, even after it heat-processes the formed resin pattern, the resin pattern manufacturing method which can manufacture the resin pattern near a rectangle or a rectangle could be provided.

It is a schematic diagram which shows the cross-sectional profile after heat processing. It is a schematic diagram which shows the upper end and lower end of the resin pattern in an example of a resin pattern. It is a schematic diagram which shows the example in the rectangularity evaluation of the upper end of a resin pattern in the cross-sectional profile after heat processing, and a lower end.

Hereinafter, the resin pattern manufacturing method of the present invention will be described in detail.
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.
Further, in the present invention, “(Component A1) a monomer unit (a1-1) having a residue in which a carboxy group or a phenolic hydroxyl group is protected with an acid-decomposable group, and a monomer unit having an epoxy group and / or an oxetanyl group. “Polymer having (a1-2)” or the like is also simply referred to as “component A” or the like, and “a monomer unit (a1-1) having a residue in which a carboxy group or a phenolic hydroxyl group is protected by an acid-decomposable group”. "Is also simply referred to as" monomer unit (a1-1) ".

(Resin pattern manufacturing method)
The resin pattern manufacturing method of the present invention includes at least steps (1) to (6) in this order.
(1) Application process for applying photosensitive resin composition on substrate (2) Solvent removal process for removing solvent from applied photosensitive resin composition (3) Activated photosensitive resin composition from which solvent has been removed (4) Development step of developing the exposed photosensitive resin composition with an aqueous developer (5) Ions generated from the surface of the developed photosensitive resin composition and plasmaized gas And / or plasma treatment step in which plasma treatment is performed by contacting with radicals (6) Heat treatment step in which heat treatment is performed on the photosensitive resin composition that has been subjected to the plasma treatment.

<Application process (process (1))>
The resin pattern manufacturing method of the present invention includes (1) a coating step of coating a photosensitive resin composition on a substrate.
In the step (1), it is preferable to form a desired dry coating film by applying the photosensitive resin composition to a predetermined substrate and removing the solvent by reducing pressure and / or heating (pre-baking).
Substrate materials that can be used in the present invention, silicon, silicon dioxide, silicon nitride, alumina, glass, glass-ceramics, gallium arsenide, indium phosphide, copper, aluminum, nickel, iron, steel, copper-silicon alloys, Indium-tin oxide coated glass; organic films such as polyimide and polyester; including but not limited to any substrate containing patterned areas of metal, semiconductor, and insulating material. Optionally, a baking step can be performed on the substrate to remove absorbed moisture before applying the photosensitive resin composition. The coating method to a board | substrate is not specifically limited, For example, methods, such as a slit coat method, a spray method, a roll coat method, a spin coat method, can be used. In the case of a large substrate, the slit coat method is particularly preferable. Here, the large substrate means a substrate having a size of 1 m or more and 5 m or less on each side.
In addition, about the photosensitive resin composition which can be used for a process (1), it mentions later.

<Solvent removal step (step (2))>
The resin pattern manufacturing method of the present invention includes (2) a solvent removal step of removing the solvent from the applied photosensitive resin composition.
In the step (2), it is preferable to form a dry coating film on the substrate by removing the solvent from the applied film by vacuum (vacuum) and / or heating. The heating conditions are preferably 70 to 120 ° C. and about 30 to 300 seconds.
Since the resin pattern manufacturing method of the present invention has good shape controllability, the resin pattern manufacturing method is suitably used for manufacturing a thick film pattern having a film thickness after removal of the solvent of 4 μm or more. The film thickness after removal of the solvent is preferably 4 to 500 μm, particularly preferably 4 to 100 μm.

<Exposure process (process (3))>
The method for producing a resin pattern of the present invention includes (3) an exposure step of exposing the photosensitive resin composition from which the solvent has been removed to a pattern with actinic rays.
In the step (3), the substrate provided with the dry coating film is irradiated with an actinic ray having a predetermined pattern. Exposure may be performed through a mask, or a predetermined pattern may be drawn directly. Actinic rays having a wavelength of 300 nm to 450 nm can be preferably used. For exposure with actinic light, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a chemical lamp, a laser generator, an LED light source, or the like can be used.
When a mercury lamp is used, actinic rays having wavelengths such as g-line (436 nm), i-line (365 nm), and h-line (405 nm) can be preferably used. Mercury lamps are preferred in that they are suitable for large area exposure compared to lasers.

When a laser is used, 343 nm and 355 nm are used for a solid (YAG) laser, 351 nm (XeF) is used for an excimer laser, and 375 nm and 405 nm are used for a semiconductor laser. Among these, 355 nm or 405 nm is more preferable from the viewpoints of stability and cost. The coating can be irradiated with the laser once or a plurality of times.
The energy density per pulse of the laser is preferably 0.1 mJ / cm ² or more and 10,000 mJ / cm ² or less. In order to sufficiently cure the coating film, 0.3 mJ / cm ² or more is more preferable, and 0.5 mJ / cm ² or more is most preferable. To prevent the coating film from being decomposed by an ablation phenomenon, 1,000 mJ / cm ² cm ² or less is more preferable, and 100 mJ / cm ² or less is most preferable. The pulse width is preferably 0.1 nsec or more and 30,000 nsec or less. In order not to decompose the color coating film due to the ablation phenomenon, 0.5 nsec or more is more preferable, 1 nsec or more is most preferable, and in order to improve the alignment accuracy during the scan exposure, 1,000 nsec or less is more preferable, Most preferred is 50 nsec or less.
Furthermore, the frequency of the laser is preferably 1 Hz or more and 50,000 Hz or less. In order to shorten the exposure processing time, 10 Hz or more is more preferable, and 100 Hz or more is most preferable. In order to improve the alignment accuracy at the time of scanning exposure, 10,000 Hz or less is more preferable, and 1,000 Hz or less is most preferable.
Compared with a mercury lamp, a laser is preferable in that the focus can be easily reduced and a mask for forming a pattern in the exposure process is not necessary and the cost can be reduced.
There are no particular restrictions on the exposure apparatus that can be used in the present invention. Commercially available exposure apparatuses include Callisto (manufactured by Buoy Technology), AEGIS (manufactured by Buoy Technology), and DF2200G (Dainippon). Screen Manufacturing Co., Ltd.) can be used. Further, devices other than those described above are also preferably used.
Moreover, irradiation light can also be adjusted through spectral filters, such as a long wavelength cut filter, a short wavelength cut filter, and a band pass filter, as needed.

  When the photosensitive composition of the first embodiment is used, PEB (post-exposure heat treatment) can be performed as necessary after the exposure step and before the development step. 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 90 ° C. or lower.

<Development process (process (4))>
The resin pattern manufacturing method of the present invention includes (4) a developing step of developing the exposed photosensitive resin composition with an aqueous developer.
In step (4), development is performed using an aqueous developer.
The aqueous developer is preferably an alkaline developer. Examples of basic compounds that can be used in the alkaline developer include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; sodium carbonate, carbonate Alkali metal carbonates such as potassium; alkali metal bicarbonates such as sodium bicarbonate and potassium bicarbonate; ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline hydroxide; sodium silicate and metasilicic acid An aqueous solution such as sodium can be used. 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 10.0 to 14.0.
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 is preferably performed for 10 to 90 seconds to form a desired pattern.

Moreover, the resin pattern manufacturing method of this invention is the re-exposure which exposes the board | substrate in which the pattern was formed with an active ray between a process (4) and a process (5) or between a process (5) and a process (6). It is preferable to include an exposure step (post-exposure step).
The exposure in the re-exposure step may be performed by the same means as in the exposure step, but in the re-exposure step, it is preferable that the entire surface of the substrate on which the photosensitive resin composition film is formed is exposed. .
A preferable exposure amount in the re-exposure step is 100 to 1,000 mJ / cm ² .

<Plasma treatment process (process (5))>
The resin pattern manufacturing method of the present invention includes (5) a plasma processing step of performing plasma processing by bringing the surface of the developed photosensitive resin composition into contact with ions and / or radicals generated from the plasmatized gas. By this plasma treatment step, the resin pattern can be prevented from flowing (heat flow) in the subsequent heat treatment step, and a resin pattern having excellent rectangularity can be obtained.
The plasma treatment in the plasma treatment step may be a plasma etching treatment or a reactive ion etching treatment, but it is preferable to perform the plasma treatment under mild conditions such that the resin pattern surface is not roughened. For example, the reduction amount of the developed photosensitive resin composition before and after the plasma treatment step is preferably 20% by weight or less, more preferably 10% by weight or less, and more preferably 5% by weight or less. Is preferable, and it is particularly preferably 1% by weight or less. The amount of change in the thickness of the developed photosensitive resin composition layer before and after the plasma treatment step is preferably 200 nm or less, more preferably 100 nm or less, and even more preferably 50 nm or less, Particularly preferably, it is 10 nm or less. Furthermore, before and after the plasma treatment step, the amount of change in the thickness of the exposed portion of the substrate is preferably 200 nm or less, more preferably 100 nm or less, further preferably 50 nm or less, and more preferably 10 nm or less. It is particularly preferred.
There is no restriction | limiting in particular about the generation | occurrence | production method of the plasma in the said plasma treatment process, For example, both a pressure reduction plasma method and an atmospheric plasma method are applicable.
The plasma processing time in the plasma processing step is not particularly limited and may be determined in consideration of each condition of the plasma processing, but is preferably 5 to 200 seconds, more preferably 5 to 60 seconds. Preferably, the time is 10 to 40 seconds. Within the above range, etching of the developed photosensitive resin composition and the substrate can be suppressed, and roughness of the resulting resin pattern and substrate surface can be suppressed.
In addition, each plasma generation condition (voltage, frequency, gas pressure, temperature, etc.) in the plasma processing step is either a reduced pressure plasma method or an atmospheric plasma method, and also considers the plasma processing apparatus to be used, What is necessary is just to determine suitably.

In the plasma treatment step, the gas to be converted into plasma is not particularly limited, and a known plasma etching gas can be used. For example, an inert gas such as helium, argon, krypton, or xenon, or a reactive gas such as O ₂ , CF ₄ , C ₂ F ₆ , N ₂ , CO ₂ , SF ₆ , or CHF ₃ can be preferably used.
Among these, a gas containing no O ₂ is more preferable, and a mixed gas of an inert gas and a reactive gas other than oxygen is more preferable.
The gas preferably contains a fluorine compound such as CF ₄ , C ₂ F ₄ , SF ₆ , or CHF ₃ , and contains a fluorinated hydrocarbon compound such as CF ₄ , C ₂ F ₆ , or CHF _3. Is more preferable, it is more preferable that CF ₄ is contained, and a mixed gas of CF ₄ and argon is particularly preferable.
Moreover, as an inert gas which may be contained in the said gas, argon is preferable.
Furthermore, the gas preferably contains 50% by weight or more of inert gas, more preferably 70% by weight or more, and still more preferably 80% by weight or more. Within the above range, etching of the developed photosensitive resin composition and the substrate can be suppressed, and roughness of the resulting resin pattern and substrate surface can be suppressed.

<Heat treatment step (step (6))>
The method for producing a resin pattern of the present invention includes (6) a heat treatment step (baking step) for heat-treating the photosensitive resin composition that has been subjected to plasma treatment.
In the step (6), a cured film can be formed by heat-treating the photosensitive resin composition subjected to the plasma treatment.
The heat treatment temperature (baking temperature) is preferably 180 to 250 ° C., and the heat treatment time is preferably 30 to 150 minutes. In order to obtain a more rectangular profile, so-called two-stage baking in which two stages of heating are performed at different temperatures can be performed. The first baking temperature is preferably 90 ° C. to 150 ° C., and the time is preferably 10 to 60 minutes. The second baking temperature is preferably 180 to 250 ° C., and the time is preferably 30 to 90 minutes. It is also possible to perform a baking process of three or more stages.
The taper angle in the cross-sectional shape of the pattern after the baking process is preferably 60 ° or more, more preferably 70 ° or more, and particularly preferably 80 ° or more.
The “taper angle” is an angle formed between the side surface of the pattern and the substrate plane on which the pattern is formed in the cross-sectional shape after the pattern is formed and the baking process is performed. When the cross-sectional shape of the side surface of the pattern is not a straight line, the cross-sectional shape is defined as an angle formed by a straight line connecting the end of the lower surface of the pattern in contact with the substrate and the end of the upper surface of the pattern and the substrate plane. When the upper surface of the pattern is not recognized, the angle is defined by the straight line connecting the point farthest from the substrate and the end of the lower surface of the pattern in contact with the substrate, and the substrate plane.
As a specific example, θ in each pattern cross-sectional shape shown in FIG. 1 is a taper angle.
In the example of the evaluation point 1 in FIG. 1, since the pattern cross-sectional shape is an arc shape and the upper surface of the pattern is not recognized, the vertex of the arc that is the point on the arc farthest from the substrate and the end of the lower surface of the pattern in contact with the substrate The angle between the straight line connecting the two and the substrate plane is θ.

  By the resin pattern manufacturing method of the present invention, a resin pattern having a rectangular shape or a profile close to a rectangular shape can be obtained even after the heat treatment step. Therefore, the resin pattern (resin pattern of the present invention) produced by the resin pattern production method of the present invention can be suitably used for a MEMS structure, an etching resist, a bump / metal post forming resist, and the like.

(MEMS structure and manufacturing method thereof, and image display device)
There are two methods for manufacturing the MEMS (Micro Electro Mechanical Systems) structure of the present invention.
One is a MEMS structure manufactured by using a resin pattern manufactured by the resin pattern manufacturing method of the present invention as a sacrificial layer at the time of stacking the structure,
The other is a MEMS structure produced using a resin pattern produced by the pattern production method of the present invention as a MEMS structure.
Note that MEMS (Micro Electro Mechanical System) refers to an electromechanical element or system or micromachine having a micro structure having a micro size or less. , Devices integrated on glass substrates, organic materials, and the like.
Examples of the MEMS shutter device and the image forming apparatus provided with the MEMS shutter device are those described in JP-T-2008-533510.

(Semiconductor element manufacturing method)
The semiconductor element manufacturing method of the present invention is a method of manufacturing a semiconductor element such as an integrated circuit by etching a substrate using the resin pattern manufactured by the resin pattern manufacturing method of the present invention as an etching resist. In the resin pattern manufacturing method of the present invention, since a rectangular resin pattern can be manufactured, the substrate to be processed can be etched cleanly.

(Plating pattern manufacturing method)
The plating pattern manufacturing method of the present invention is a method of manufacturing a plating pattern by plating using the resin pattern manufactured by the resin pattern manufacturing method of the present invention as a mold. Since the resin pattern production method of the present invention can produce a rectangular and thick resin pattern, a plating pattern for bumps and metal posts can be suitably produced.
The bump is an electrode used when connecting a large scale integrated circuit (LSI) or the like to an electronic device, and is described in detail in Japanese Patent No. 4544219.

(Photosensitive resin composition)
Hereinafter, each component which comprises the photosensitive resin composition is demonstrated.
In addition, in the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what has a substituent with what does not have 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).
The photosensitive composition used for this invention will not be specifically limited if it has photosensitivity and developability. It preferably has a property of being cured by heat. Among these, any of the following three embodiments is preferable.

In the first embodiment, which is a preferred embodiment of the photosensitive resin composition, (Component A1) (a1-1) a monomer unit having a residue in which a carboxy group or a phenolic hydroxyl group is protected with an acid-decomposable group; a1-2) A photosensitive resin composition comprising a polymer having a monomer unit having an epoxy group and / or an oxetanyl group, (Component B1) a photoacid generator, and (Component C1) a solvent.
Component A1 contains (a1-3) a monomer unit having a ring structure and / or (a1-4) a monomer unit having a carboxy group or a hydroxyl group, in addition to the monomer units (a1) and (a2). Is preferred.
Component A may contain monomer units (a1-5) other than the monomer units (a1-1) to (a1-4).
The “monomer unit” in the present invention includes not only a structural unit formed from one monomer molecule but also a structural unit obtained by modifying a structural unit formed from one monomer molecule by a polymer reaction or the like.
Moreover, the residue in which the carboxy group or the phenolic hydroxyl group is protected with an acid-decomposable group may generate a carboxy group or a phenolic hydroxyl group by decomposing (deprotecting) the acid-decomposable group with an acid. it can.

(Component A1) Polymer having monomer unit (a1-1) and monomer unit (a1-2) In the photosensitive resin composition, (Component A1) (a1-1) carboxy group or phenolic hydroxyl group is acid-decomposed. It is preferable to contain a polymer having a monomer unit having a residue protected with a functional group and a monomer unit having (a1-2) an epoxy group and / or an oxetanyl group.
Component A1 is preferably a resin that is insoluble in alkali and becomes alkali-soluble when the acid-decomposable group in the monomer unit (a1-1) is decomposed.
The term “alkali-soluble” in the present invention refers to a coating film (thickness 4 μm) of the compound (resin) formed by applying a solution of the compound (resin) on a substrate and heating at 90 ° C. for 2 minutes. ) In a 0.4 wt% tetramethylammonium hydroxide aqueous solution at 23 ° C. is 0.01 μm / second or more. “Alkali insoluble” means that the solution of the compound (resin) is a substrate. The dissolution rate of a coating film (thickness: 4 μm) of the compound (resin) formed by coating on the substrate and heating at 90 ° C. for 2 minutes in a 0.4 wt% tetramethylammonium hydroxide aqueous solution at 23 ° C. It means less than 0.01 μm / second, preferably less than 0.005 μm / second.

The weight average molecular weight (Mw) of component A1 is preferably 5,000 or more, more preferably 12,000 or more, still more preferably 20,000 or more, and 1,000,000. Or less, more preferably 80,000 or less, and still more preferably 60,000 or less. Within the above range, a good rectangle or a profile close to a rectangle can be obtained even after the baking step. Further, when the weight average molecular weight is 12,000 or more, the shape change in the baking process is small, and in particular, a rectangle or a profile close to a rectangle can be obtained. Further, when the weight average molecular weight is 80,000 or less, the pattern formability during development is excellent.
The weight average molecular weight is a value in terms of polystyrene measured by GPC (gel permeation chromatography). It is preferable to use THF as the solvent and TSKgel SuperHZ3000 and TSKgel SuperHZM-M (both manufactured by Tosoh Corporation) as the column.

Component A1 is preferably an acrylic polymer.
The “acrylic polymer” in the present invention is an addition polymerization type resin, is a polymer containing a monomer unit derived from (meth) acrylic acid or an ester thereof, and is derived from (meth) acrylic acid or an ester thereof. You may have monomer units other than a monomer unit, for example, the monomer unit derived from styrenes, the monomer unit derived from a vinyl compound, etc. In addition, Component A1 may include both a monomer unit derived from (meth) acrylic acid and a monomer unit derived from (meth) acrylic acid ester.
In the present specification, the “monomer unit derived from (meth) acrylic acid or its ester” is also referred to as “acrylic monomer unit”. (Meth) acrylic acid is a generic term for methacrylic acid and acrylic acid.
Hereinafter, each monomer unit such as the monomer unit (a1-1) and the monomer unit (a1-2) will be described.

<Monomer unit (a1-1) having a residue in which a carboxy group or a phenolic hydroxyl group is protected with an acid-decomposable group>
Component A has at least a monomer unit (a1-1) having a residue in which a carboxy group or a phenolic hydroxyl group is protected with an acid-decomposable group.
By having the monomer unit (a1-1) in Component A, a highly sensitive photosensitive resin composition can be obtained. A monomer unit having a residue in which a carboxy group is protected with an acid-decomposable group is characterized by faster development than a monomer unit having a residue in which a phenolic hydroxyl group is protected with an acid-decomposable group. Therefore, a monomer unit having a residue in which a carboxy group is protected with an acid-decomposable group is preferable for rapid development. Conversely, when it is desired to delay development, it is preferable to use a monomer unit having a residue in which a phenolic hydroxyl group is protected with an acid-decomposable group.

[Monomer unit (a1-1-1) having a residue in which a carboxy group is protected with an acid-decomposable group]
-Monomer unit having a carboxy group-
Examples of the monomer unit having a carboxy group include monomer units derived from an unsaturated carboxylic acid having at least one carboxy group in the molecule, such as an unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, and unsaturated tricarboxylic acid. Is mentioned.
Examples of the unsaturated carboxylic acid used for obtaining the monomer unit having a carboxy group include those listed below. That is, examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid. Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid. Moreover, the acid anhydride may be sufficient as unsaturated polyhydric carboxylic acid used in order to obtain the monomer unit which has a carboxy group. Specific examples include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. The unsaturated polyvalent carboxylic acid may be a mono (2-methacryloyloxyalkyl) ester of a polyvalent carboxylic acid. For example, succinic acid mono (2-acryloyloxyethyl), succinic acid mono (2 -Methacryloyloxyethyl), mono (2-acryloyloxyethyl) phthalate, mono (2-methacryloyloxyethyl) phthalate and the like.
Further, the unsaturated polyvalent carboxylic acid may be a mono (meth) acrylate of a dicarboxy polymer at both ends, and examples thereof include ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate.
As the unsaturated carboxylic acid, acrylic acid-2-carboxyethyl ester, methacrylic acid-2-carboxyethyl ester, maleic acid monoalkyl ester, fumaric acid monoalkyl ester, 4-carboxystyrene and the like can also be used.
Among these, from the viewpoint of developability, in order to form a monomer unit having a carboxy group, it is preferable to use acrylic acid, methacrylic acid, or an anhydride of unsaturated polyvalent carboxylic acid, and acrylic acid or methacrylic acid. More preferably, it is used.
The monomer unit which has a carboxy group may be comprised by 1 type individually, and may be comprised by 2 or more types.

The monomer unit having a carboxy group may be a monomer unit obtained by reacting a monomer unit having a hydroxyl group with an acid anhydride.
As the acid anhydride, known ones can be used, and specific examples include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride and the like. Examples include basic acid anhydrides; acid anhydrides such as trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic acid anhydride, and biphenyl tetracarboxylic acid anhydride. Among these, phthalic anhydride, tetrahydrophthalic anhydride, or succinic anhydride is preferable from the viewpoint of developability.
The reaction rate of the acid anhydride with respect to the hydroxyl group is preferably 10 to 100 mol%, more preferably 30 to 100 mol%, from the viewpoint of developability.

-Monomer unit (a1-1-1) having a residue in which a carboxy group is protected with an acid-decomposable group-
The monomer unit (a1-1-1) having a residue in which a carboxy group is protected with an acid-decomposable group is preferably the acid-decomposable property described below in detail. A monomer unit having a residue protected by a group.
As the acid-decomposable group, known acid-decomposable groups in the positive resist for KrF and the positive resist for ArF can be used and are not particularly limited. Conventionally, as an acid-decomposable group, a group that is relatively easily decomposed by an acid (for example, an acetal functional group such as a tetrahydropyranyl group) or a group that is relatively difficult to be decomposed by an acid (for example, a t-butyl ester group, t -T-butyl functional groups such as butyl carbonate groups) are known.
Among these acid-decomposable groups, the basic physical properties of the resist, in particular the sensitivity and pattern, are residues having a residue in which the carboxy group is protected with an acetal or a residue in which the carboxy group is protected with a ketal From the viewpoints of shape, contact hole formability, and storage stability of the photosensitive resin composition, it is preferable. Furthermore, among acid-decomposable groups, it is more preferable from the viewpoint of sensitivity that the carboxy group is a residue protected with an acetal or ketal represented by the following formula (a1-1). In addition, when the carboxy group is an acetal or ketal-protected residue represented by the following formula (a1-1), the entire residue is —C (═O) —O—CR ¹ R ² ( OR ³ ).

（式（ａ１−１）中、Ｒ¹及びＲ²は、それぞれ独立に水素原子又はアルキル基を表し、ただし、Ｒ¹とＲ²とが共に水素原子の場合を除く。Ｒ³は、アルキル基を表す。Ｒ¹又はＲ²と、Ｒ³とが連結して環状エーテルを形成してもよい。また、波線部分は、他の構造との結合位置を表す。）

(In formula (a1-1), R ¹ and R ² each independently represents a hydrogen atom or an alkyl group, except that R ¹ and R ² are both hydrogen atoms. R ³ represents an alkyl group. R ¹ or R ² and R ³ may be linked to form a cyclic ether, and the wavy line represents the bonding position with another structure.)

In formula (a1-1), R ^{1 to} R ³ each independently represents a hydrogen atom or an alkyl group, and the alkyl group may be linear, branched or cyclic. Here, both R ¹ and R ² do not represent a hydrogen atom, and at least one of R ¹ and R ² represents an alkyl group.
In formula (a1-1), when R ¹ , R ² and R ³ represent an alkyl group, the alkyl group may be linear, branched or cyclic.
The linear or branched alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms. . Specifically, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, neopentyl group, n Examples include -hexyl group, texyl group (2,3-dimethyl-2-butyl group), n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, and n-decyl group.
The cyclic alkyl group preferably has 3 to 12 carbon atoms, more preferably 4 to 8 carbon atoms, and still more preferably 4 to 6 carbon atoms. Examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, and an isobornyl group.

The alkyl group may have a substituent, and examples of the substituent include a halogen atom, an aryl group, and an alkoxy group. When it has a halogen atom as a substituent, R ¹ , R ² and R ³ become a haloalkyl group, and when it has an aryl group as a substituent, R ¹ , R ² and R ³ become an aralkyl group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and among these, a fluorine atom or a chlorine atom is preferable.
Moreover, as said aryl group, a C6-C20 aryl group is preferable and a C6-C12 aryl group is more preferable. Specific examples include a phenyl group, an α-methylphenyl group, and a naphthyl group.
As the aralkyl group, an aralkyl group having 7 to 32 carbon atoms is preferable, and an aralkyl group having 7 to 20 carbon atoms is more preferable. Specific examples include a benzyl group, an α-methylbenzyl group, a phenethyl group, and a naphthylmethyl group.
As the alkoxy group, an alkoxy group having 1 to 6 carbon atoms is preferable, an alkoxy group having 1 to 4 carbon atoms is more preferable, and a methoxy group or an ethoxy group is further preferable.
In addition, when the alkyl group is a cycloalkyl group, the cycloalkyl group may have a linear or branched alkyl group having 1 to 10 carbon atoms as a substituent, and the alkyl group is linear Or a branched alkyl group, it may have a cycloalkyl group having 3 to 12 carbon atoms as a substituent.
These substituents may be further substituted with the above substituents.

In the formula (a1-1), when R ¹ , R ² and R ³ represent an aryl group, the aryl group preferably has 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms. preferable. The aryl group may have a substituent, and preferred examples of the substituent include an alkyl group having 1 to 6 carbon atoms. Examples of the aryl group include a phenyl group, a tolyl group, a silyl group, a cumenyl group, and a 1-naphthyl group.
R ¹ , R ² and R ³ can be bonded to each other to form a ring together with the carbon atom to which they are bonded. Examples of the ring structure when R ¹ and R ² , R ¹ and R ³ or R ² and R ³ are bonded include, for example, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a tetrahydrofuranyl group, an adamantyl group, and a tetrahydro group. A pyranyl group etc. can be mentioned. Of these, a tetrahydrofuranyl group is preferred.
In formula (a1-1), either R ¹ or R ² is preferably a hydrogen atom or a methyl group.

  As the radical polymerizable monomer used for forming the monomer unit having a residue represented by the formula (a1-1), a commercially available one may be used, or one synthesized by a known method may be used. You can also. For example, as shown below, it can be synthesized by reacting (meth) acrylic acid with vinyl ether in the presence of an acid catalyst.

R ¹¹ represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or a methyl group.
R ¹² and R ¹³ have the same meaning as R ² in formula (a1-1) as —CH (R ¹² ) (R ¹³ ), R ¹⁴ has the same meaning as R ¹ in formula (a1-1), R ¹⁵ has the same meaning as R ³ in formula (a1-1), and preferred ranges thereof are also the same.
In the above synthesis, (meth) acrylic acid may be previously copolymerized with other monomers and then reacted with vinyl ether in the presence of an acid catalyst.

  Preferable specific examples of the monomer unit (a1-1-1) having a residue in which a carboxy group is protected with an acid-decomposable group include the following monomer units. R represents a hydrogen atom or a methyl group.

[Monomer unit having a residue in which a phenolic hydroxyl group is protected with an acid-decomposable group (a1-1-2)]
-Monomer unit having a phenolic hydroxyl group-
Examples of the monomer unit having a phenolic hydroxyl group include a hydroxystyrene monomer unit and a monomer unit in a novolac resin. Among the monomer units having a phenolic hydroxyl group, the monomer unit represented by the formula (a1-2) is preferable from the viewpoints of transparency and sensitivity.

（式（ａ１−２）中、Ｒ²⁰は水素原子又はメチル基を表し、Ｒ²¹は単結合又は二価の連結基を表し、Ｒ²²はハロゲン原子又はアルキル基を表し、ａは１〜５の整数を表し、ｂは０〜４の整数を表し、ａ＋ｂは５以下である。なお、Ｒ²²が２以上存在する場合、これらのＲ²²は相互に異なっていてもよいし同じでもよい。）

(In formula (a1-2), R ²⁰ represents a hydrogen atom or a methyl group, R ²¹ represents a single bond or a divalent linking group, R ²² represents a halogen atom or an alkyl group, and a represents 1 to 5 And b represents an integer of 0 to 4, and a + b is 5 or less, and when R ²² is 2 or more, these R ²² may be different from each other or the same. )

In formula (a1-2), R ²⁰ represents a hydrogen atom or a methyl group, and is preferably a methyl group.
R ²¹ in formula (a1-2) represents a single bond or a divalent linking group. A single bond is preferable because the sensitivity can be improved and the transparency of the cured film can be further improved. The divalent linking group for R ²¹ may be exemplified alkylene groups, specific examples R ²¹ is an alkylene group, a methylene group, an ethylene group, a propylene group, isopropylene group, n- butylene group, isobutylene group, tert -Butylene group, pentylene group, isopentylene group, neopentylene group, hexylene group, etc. are mentioned. Among these, R ²¹ is preferably a single bond, a methylene group, or an ethylene group. The divalent linking group may have a substituent, and examples of the substituent include a halogen atom, a hydroxyl group, and an alkoxy group.
Further, a in the formula (a1-2) represents an integer of 1 to 5, but a is preferably 1 or 2 from the viewpoint of the effect of the present invention and easy production. Is more preferably 1.
Further, the bonding position of the hydroxyl group in the benzene ring is preferably bonded to the 4-position when the carbon atom bonded to R ²¹ is the reference (first position).
R ²² in formula (a1-2) is a halogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms. Specific examples include fluorine atom, chlorine atom, bromine atom, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group and the like. It is done. Among these, a chlorine atom, a bromine atom, a methyl group, or an ethyl group is preferable from the viewpoint of easy production.
B represents 0 or an integer of 1 to 4;

Among the monomer units having a phenolic hydroxyl group, when R ²¹ is not an alkylene group in the formula (a1-2), the monomer unit represented by the formula (a1-2 ′) is a viewpoint of transparency and sensitivity. To more preferable. Preferred examples of the linking group for R ²¹ include an alkyleneoxycarbonyl group (from the main chain side of the copolymer) in addition to the alkylene group. In this case, the monomer unit having a phenolic hydroxyl group is represented by the following formula ( a1-2 ′).

（式（ａ１−２’）中、Ｒ³⁰は水素原子又はメチル基を表し、Ｒ³³は二価の連結基を表し、Ｒ³²はハロゲン原子又はアルキル基を表し、ａは１〜５の整数を表し、ｂは０〜４の整数を表し、ａ＋ｂは５以下である。なお、Ｒ³²が２以上存在する場合、これらのＲ²²は相互に異なっていてもよいし同じでもよい。）

(In the formula (a1-2 ′), R ³⁰ represents a hydrogen atom or a methyl group, R ³³ represents a divalent linking group, R ³² represents a halogen atom or an alkyl group, and a is an integer of 1 to 5. B represents an integer of 0 to 4, and a + b is 5 or less, and when R ³² is 2 or more, these R ²² may be different or the same.

In formula (a1-2 ′), R ³⁰ has the same meaning as R ²⁰ in formula (a1-2), R ³² has the same meaning as R ²² in formula (a1-2), and a and b have the formula (a1 -2) are the same as a and b in -2. The preferable range is also the same.
In the formula (a1-2 ′), R ³³ represents a divalent linking group, and an alkylene group can be preferably exemplified. The alkylene group may be linear or branched and preferably has 2 to 6 carbon atoms, and is an ethylene group, a propylene group, an isopropylene group, an n-butylene group, a tert-butylene group, or a pentylene. Group, isopentylene group, neopentylene group, hexylene group and the like. Further, the divalent linking group may have a substituent, and examples of the substituent include a halogen atom, a hydroxyl group, and an alkoxy group. Among these, R ³³ is preferably an ethylene group, a propylene group, or a 2-hydroxypropylene group from the viewpoint of sensitivity.

-Monomer unit (a1-1-2) having a residue in which a phenolic hydroxyl group is protected with an acid-decomposable group-
The monomer unit having a residue in which a phenolic hydroxyl group is protected with an acid-decomposable group is a residue in which the phenolic hydroxyl group of the monomer unit having a phenolic hydroxyl group is protected by an acid-decomposable group described in detail below. It is a monomer unit having.
As the acid-decomposable group, a known group can be used as described above, and is not particularly limited. Among acid-decomposable groups, the basic physical properties of the resist, in particular the sensitivity and pattern shape, are residues having a phenolic hydroxyl group protected with an acetal or a residue having a phenolic hydroxyl group protected with a ketal. From the viewpoint of storage stability of the photosensitive resin composition and formability of the contact hole. Furthermore, among the acid-decomposable groups, the phenolic hydroxyl group is more preferably a residue protected with an acetal or ketal represented by the above formula (a1-1) from the viewpoint of sensitivity. In addition, when the phenolic hydroxyl group is an acetal or ketal-protected residue represented by the formula (a1-1), the residue as a whole is —Ar—O—CR ¹ R ² (OR ³ ). It has a structure. Ar represents an arylene group.
Preferred examples of the acetal ester structure for protecting the phenolic hydroxyl group include a combination of R ¹ = R ² = R ³ = methyl group, R ¹ = R ² = methyl group, and R ³ = benzyl group.

  Examples of the radical polymerizable monomer used to form a monomer unit having a residue in which a phenolic hydroxyl group is protected with an acetal or ketal include, for example, a 1-alkoxyalkyl protector of hydroxystyrene, Protected tetrahydropyranyl, 1-alkoxyalkyl protected α-methylhydroxystyrene, tetrahydropyranyl protected α-methyl-hydroxystyrene, 1-alkoxyalkyl protected 4-hydroxyphenyl methacrylate, 4-hydroxyphenyl methacrylate Tetrahydropyranyl protected product, 4-hydroxybenzoic acid (1-methacryloyloxymethyl) ester 1-alkoxyalkyl protected, 4-hydroxybenzoic acid (1-methacryloyloxymethyl) ester tetra Protected hydropyranyl, 1-alkoxyalkyl protected 4-hydroxybenzoic acid (2-methacryloyloxyethyl) ester, tetrahydropyranyl protected 4-hydroxybenzoic acid (2-methacryloyloxyethyl) ester, 4-hydroxybenzoic acid 1-alkoxyalkyl protector of (3-methacryloyloxypropyl) ester, tetrahydropyranyl protector of 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester, 4-hydroxybenzoic acid (3-methacryloyloxy-2-hydroxy) 1-alkoxyalkyl protector of propyl) ester, tetrahydropyranyl protector of 4-hydroxybenzoic acid (3-methacryloyloxy-2-hydroxypropyl) ester, and the like.

  As an acetal protecting group and a ketal protecting group for a phenolic hydroxyl group, the formula (a1-1) is preferable. These can be used alone or in combination of two or more.

  Preferable specific examples of the monomer unit (a1-1-2) include the following monomer units, but the present invention is not limited thereto. In the following monomer unit, R represents a hydrogen atom or a methyl group.

  From the viewpoint of sensitivity, the content of the monomer unit (a1-1) in Component A1 is preferably 3 to 70 mol%, more preferably 5 to 60 mol%, and more preferably 10 to 50 mol based on all monomer units of Component A1. % Is more preferable. On the other hand, from the viewpoint of reducing profile deterioration due to deprotection shrinkage, the content of the monomer unit (a1-1) is preferably 45 mol% or less, and considering both sensitivity and rectangularity, 10 It is particularly preferable that the amount be in the range of -45 mol%.

<Monomer unit having epoxy group and / or oxetanyl group (a1-2)>
Component A has a monomer unit (a1-2) having an epoxy group and / or an oxetanyl group. Component A may have both a monomer unit having an epoxy group and a monomer unit having an oxetanyl group.
The group having an epoxy group is not particularly limited as long as it has an epoxy ring, but a glycidyl group and a 3,4-epoxycyclohexylmethyl group can be preferably exemplified.
The group having an oxetanyl group is not particularly limited as long as it has an oxetane ring, but a (3-ethyloxetane-3-yl) methyl group can be preferably exemplified.
The monomer unit (a1-2) may have at least one epoxy group or oxetanyl group in one monomer unit, one or more epoxy groups and one or more oxetanyl groups, two or more epoxy groups. Group, or may have two or more oxetanyl groups, and is not particularly limited, but preferably has a total of 1 to 3 epoxy groups and / or oxetanyl groups, and a total of epoxy groups and / or oxetanyl groups It is more preferable to have one or two, and it is still more preferable to have one epoxy group or one oxetanyl group.

Specific examples of the radical polymerizable monomer used to form the monomer unit having an epoxy group include, for example, glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, and glycidyl α-n-propyl acrylate. Glycidyl α-n-butyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, acrylate-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, cycloaliphatic described in paragraphs 0031 to 0035 of Japanese Patent No. 4168443 Compounds containing an epoxy skeleton It is.
Examples of the radical polymerizable monomer used to form a monomer unit having an oxetanyl group include, for example, (meth) acrylic acid having an oxetanyl group described in paragraphs 0011 to 0016 of JP-A No. 2001-330953. Examples include esters.

As an example of the radically polymerizable monomer used for forming the monomer unit (a1-2), a monomer containing a methacrylic ester structure and a monomer containing an acrylic ester structure are preferable.
Among these monomers, more preferred are glycidyl methacrylate, glycidyl acrylate, compounds containing an alicyclic epoxy skeleton described in paragraphs 0034 to 0035 of Japanese Patent No. 4168443, and JP-A No. 2001-330953. Examples thereof include (meth) acrylic acid esters having an oxetanyl group described in paragraphs 0011 to 0016 of the publication.
Particularly preferable from the viewpoint of heat-resistant transparency is a monomer unit derived from either (3-ethyloxetane-3-yl) methyl acrylate or methyl (3-ethyloxetane-3-yl) methacrylate. is there.
These monomer units (a1-2) can be used individually by 1 type or in combination of 2 or more types.

  Preferable specific examples of the monomer unit (a1-2) include the following monomer units.

  The content of the monomer unit (a1-2) in Component A is preferably 20 to 55 mol%, more preferably 25 to 55 mol%, particularly preferably 25 to 50 mol%, based on all monomer units of Component A. By containing the monomer unit (a1-2) at the above ratio, the physical properties of the cured film are improved.

<Monomer unit having a ring structure (a1-3)>
Component A1 preferably contains a monomer unit (a1-3) having a ring structure from the viewpoint of improving dry etching resistance and chemical resistance.
Examples of the monomer that forms the monomer unit (a1-3) include (meth) acrylic acid such as styrenes, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, and cyclohexyl (meth) acrylate. Examples thereof include cyclic alkyl esters and unsaturated aromatic compounds.
Preferred examples of the monomer unit (a1-3) having a ring structure include monomer units represented by the following formula (a3-1) or formula (a3-2).

（式中、Ｒ^Aは水素原子又は炭素原子数１〜６のアルキル基を表す。）

(In the formula, R ^A represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)

R ^A in the formula (a3-1) is preferably a hydrogen atom or a methyl group, particularly preferably a hydrogen atom, from the viewpoint of the uniformity of the polymerization rate of each monomer during polymerization.

（式中、Ｒ^Bは水素原子又はメチル基を表し、Ｘは単結合又は炭素原子数１〜４のアルキ
レン基を表し、環Ａはシクロペンタン環又はシクロペンテン環を表し、環Ａを有していても、有していなくともよい。）

(In the formula, R ^B represents a hydrogen atom or a methyl group, X represents a single bond or an alkylene group having 1 to 4 carbon atoms, Ring A represents a cyclopentane ring or a cyclopentene ring, and has ring A. Or do not have to.)

R ^B in the formula (a3-2), from the viewpoint of the uniformity of the polymerization rate of each monomer during the polymerization is preferably a methyl group.
X in the formula (a3-2) is preferably a single bond, a methylene group or an ethylene group, and more preferably a single bond.
Ring A in formula (a3-2) is preferably a cyclopentane ring.
The formula (a3-2) preferably has a ring A. The position of the double bond of the cyclopentene ring in ring A is not particularly limited and may be any position.

  The content of the monomer unit (a1-3) in Component A is preferably from 1 to 30 mol%, more preferably from 5 to 25 mol%, particularly preferably from 10 to 20 mol%, based on all monomer units of Component A. By including the monomer unit (a1-3) at the above ratio, the resulting pattern is excellent in dry etching resistance and chemical resistance.

<Monomer unit having carboxy group or hydroxyl group (a1-4)>
Component A1 preferably has a monomer unit (a1-4) having a carboxy group or a hydroxyl group from the viewpoint of developability.
The monomer unit (a1-4) is preferably introduced in a range where the component A is not alkali-soluble. The content of the monomer unit (a1-4) in Component A is preferably 2 to 20 mol%, more preferably 2 to 15 mol%, particularly preferably 3 to 15 mol%, based on all monomer units of Component A. By containing the monomer unit (a1-4) in the above proportion, high sensitivity is obtained and developability is also improved.

[Monomer unit having carboxy group (a1-4-1)]
As the monomer unit (a1-4-1) having a carboxy group, the “carboxy group has a —carboxy group” described in the monomer unit (a1-1-2) having a residue protected with an acid-decomposable group. Those similar to the “monomer unit” can be used.
Among these, from the viewpoint of developability, it is preferable to use acrylic acid or methacrylic acid in order to form the monomer unit (a1-4-1) having a carboxy group.

[Monomer unit having a phenolic hydroxyl group (a1-4-2)]
Examples of the monomer unit (a1-4) having a hydroxyl group include a monomer unit (a1-4-2) having a phenolic hydroxyl group.
Examples of the radical polymerizable monomer used for forming the monomer unit (a1-4-2) having a phenolic hydroxyl group include hydroxystyrenes such as p-hydroxystyrene and α-methyl-p-hydroxystyrene. And compounds described in paragraphs 0011 to 0016 of JP-A-2008-40183, 4-hydroxybenzoic acid derivatives described in paragraphs 0007 to 0010 of Japanese Patent No. 2888454, and 4-hydroxybenzoic acid and glycidyl methacrylate Preferred examples include addition reaction products, addition reaction products of 4-hydroxybenzoic acid and glycidyl acrylate, and the like.

  Among radical polymerizable monomers used for forming a monomer unit (a1-4-2) having a phenolic hydroxyl group, methacrylic acid, acrylic acid, described in paragraphs 0011 to 0016 of JP-A-2008-40183 Compound, 4-hydroxybenzoic acid derivatives described in paragraphs 0007 to 0010 of Japanese Patent No. 2888454, addition reaction product of 4-hydroxybenzoic acid and glycidyl methacrylate, 4-hydroxybenzoic acid and glycidyl acrylate Addition reactants are more preferred, but methacrylic acid and acrylic acid are particularly preferred from the viewpoint of transparency. These monomer units can be used singly or in combination of two or more.

[Monomer unit having a hydroxyl group other than phenolic hydroxyl group (a1-4-3)]
As the monomer unit (a1-4-3) having a hydroxyl group other than the phenolic hydroxyl group, any monomer unit having a hydroxyl group can be used, and a hydroxyl group-containing (meth) acrylic acid is preferable. Examples thereof include monomer units derived from esters, (meth) acrylic acid esters of alkyl group-terminated polyalkylene glycols, (meth) acrylic acid esters of aryl group-terminated polyalkylene glycols, and the like.

  Examples of the hydroxyl group-containing (meth) acrylic acid ester include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 2,3 (meth) acrylic acid. -Hydroxyalkyl esters of (meth) acrylic acid such as dihydroxypropyl, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, poly (ethylene glycol / propylene glycol)- Mono (meth) acrylate, polyethylene glycol / polypropylene glycol-mono (meth) acrylate, poly (ethylene glycol / tetramethylene glycol) -mono (meth) acrylate, poly (propylene glycol) Le tetramethylene glycol) - mono (meth) acrylate, propylene glycol polybutylene glycol - may be mentioned as preferred examples of the mono (meth) acrylate.

Examples of (meth) acrylic acid esters of alkyl group-terminated polyalkylene glycols include methoxypolyethylene glycol (meth) acrylate, octoxypolyethylene glycol-polypropylene glycol (meth) acrylate, lauroxypolyethylene glycol (meth) acrylate, stearoxypolyethylene Glycol (meth) acrylate can be mentioned as a preferred example.
Examples of the (meth) acrylic acid ester of an aryl group-terminated polyalkylene glycol include, for example, phenoxy polyethylene glycol (meth) acrylate, phenoxy polyethylene glycol-polypropylene glycol (meth) acrylate, nonylphenoxy-polyethylene glycol (meth) acrylate, and nonylphenoxy-polypropylene. Preferred examples include glycol (meth) acrylate and nonylphenoxy-poly (ethylene glycol-propylene glycol) (meth) acrylate.

  In the monomer unit (a1-4-3), the number of hydroxyl groups is preferably 1 to 30, more preferably 1 to 15, and particularly preferably 1 to 5.

  A monomer unit (a1-4) can be used individually by 1 type or in combination of 2 or more types.

The content of the monomer unit (a1-4) in Component A is preferably 0.5 to 30 mol%, more preferably 0.5 to 25 mol%, and more preferably 1 to 25 mol% with respect to all monomer units of Component A. Is particularly preferred.
The content of the monomer unit (a1-4) in Component A is preferably 3 to 30% by weight, more preferably 3 to 25% by weight, and particularly preferably 5 to 25% by weight with respect to the total weight of Component A. . By incorporating the monomer unit (a1-4) at the above ratio, the developability is improved and a highly sensitive photosensitive composition can be obtained. In particular, a highly sensitive photosensitive resin composition can be obtained by combining the monomer unit (a2) and the monomer unit (a1-4).

<Other monomer units (a1-5)>
Component A may contain monomer units (a1-5) other than the monomer units (a1-1) to (a1-4) as long as the effects of the present invention are not hindered.
Examples of the radical polymerizable monomer used for forming the monomer unit (a1-5) include the compounds described in paragraphs 0021 to 0024 of JP-A No. 2004-264623 (provided above The monomers that form the monomer units (a1-1) to (a1-4) are excluded.
Component A may have one type of monomer unit (a1-5) alone or two or more types.

The content of the monomer unit (a1-5) in Component A1 is preferably 0 to 40 mol% with respect to all the monomer units of Component A1.
Moreover, when component A contains a monomer unit (a1-5), 1-40 mol% is preferable with respect to all the monomer units of component A1, and content of the monomer unit (a5) in component A1 is 5-30. Mole% is more preferable, and 5 to 25 mol% is particularly preferable.
In addition, the weight average molecular weight in this invention is a polystyrene conversion weight average molecular weight by gel permeation chromatography (GPC).

Further, the method for introducing each monomer unit contained in Component A1 may be a polymerization method, a polymer reaction method, or a combination of these two methods.
Component A1 can be used singly or in combination of two or more in the photosensitive resin composition.

The content of component A1 in the photosensitive resin composition is preferably 20 to 99% by weight, more preferably 40 to 97% by weight, based on the total solid content of the photosensitive resin composition. 60 to 95% by weight is more preferable. When the content is within this range, the pattern formability upon development is good. In addition, the solid content amount of the photosensitive resin composition represents an amount excluding volatile components such as a solvent.
In addition, in the said photosensitive resin composition, you may use together resin other than component A1 in the range which does not prevent the effect of this invention. However, the content of the resin other than the component A1 is preferably smaller than the content of the component A1 from the viewpoint of developability.

(Component B1) Photoacid Generator The photosensitive resin composition that can be used in the present invention preferably contains (Component B1) a photoacid generator.
Component B1 is preferably a compound that reacts with actinic rays having a wavelength of 300 nm or more, preferably 300 to 450 nm and generates an acid, but is not limited to its chemical structure. Further, a photoacid generator that is not directly sensitive to an actinic ray having a wavelength of 300 nm or more can also be used as a sensitizer if it is a compound that reacts with an actinic ray having a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer. It can be preferably used in combination.
Component B1 is preferably a photoacid generator that generates an acid having a pKa of 4 or less, and more preferably a photoacid generator that generates an acid having a pKa of 3 or less.
Examples of the photoacid generator include trichloromethyl-s-triazines, sulfonium salts and iodonium salts, quaternary ammonium salts, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. Among these, it is preferable to use an oxime sulfonate compound from the viewpoint of high sensitivity. These photoacid generators can be used singly or in combination of two or more.

Specific examples of these include the following.
As trichloromethyl-s-triazines, 2- (3-chlorophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -bis (4,6-trichloromethyl)- s-triazine, 2- (4-methylthiophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methoxy-β-styryl) -bis (4,6-trichloromethyl) -s -Triazine, 2-piperonyl-bis (4,6-trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -bis (4,6-trichloromethyl) -s-triazine, 2- [2- (5-Methylfuran-2-yl) ethenyl] -bis (4,6-trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methyl) Butylphenyl) ethenyl] - bis (4,6-trichloromethyl) -s-triazine, or 2- (4-methoxynaphthyl) - bis (4,6-trichloromethyl) -s-triazine.

  Examples of diaryliodonium salts include diphenyliodonium trifluoroacetate, diphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoroacetate, phenyl-4- (2′-hydroxy-1) '-Tetradecaoxy) phenyliodonium trifluoromethanesulfonate, 4- (2'-hydroxy-1'-tetradecaoxy) phenyliodonium hexafluoroantimonate, or phenyl-4- (2'-hydroxy-1'-) Tetradecaoxy) phenyliodonium p-toluenesulfonate and the like.

  Examples of triarylsulfonium salts include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyldiphenylsulfonium trifluoroacetate, 4-phenylthiophenyldiphenylsulfonium trifluoro. Lomethanesulfonate or 4-phenylthiophenyldiphenylsulfonium trifluoroacetate.

  As quaternary ammonium salts, tetramethylammonium butyltris (2,6-difluorophenyl) borate, tetramethylammonium hexyltris (p-chlorophenyl) borate, tetramethylammonium hexyltris (3-trifluoromethylphenyl) borate, benzyl Dimethylphenylammonium butyltris (2,6-difluorophenyl) borate, benzyldimethylphenylammonium hexyltris (p-chlorophenyl) borate, benzyldimethylphenylammonium hexyltris (3-trifluoromethylphenyl) borate and the like.

  Examples of the diazomethane derivative include bis (cyclohexylsulfonyl) diazomethane, bis (t-butylsulfonyl) diazomethane, and bis (p-toluenesulfonyl) diazomethane.

  Examples of imide sulfonate derivatives include trifluoromethylsulfonyloxybicyclo [2.2.1] hept-5-ene-dicarboximide, succinimide trifluoromethyl sulfonate, phthalimido trifluoromethyl sulfonate, N-hydroxynaphthalimide methane sulfonate, N- Hydroxy-5-norbornene-2,3-dicarboximide propane sulfonate and the like.

  The photosensitive resin composition preferably contains an oxime sulfonate compound having at least one oxime sulfonate residue represented by the following formula (1) as (Component B1) a photoacid generator. Note that the wavy line represents the bonding position with another chemical structure.

The oxime sulfonate compound having at least one oxime sulfonate residue represented by the formula (1) is preferably a compound represented by the following formula (2).
^{R 1A -C (R 2A) =} N-O-SO 2 -R 3A (2)

In the formula (2), R ^1A is an alkyl group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, a phenyl group, a biphenyl group, a naphthyl group, a 2-furyl group, or a 2-thienyl group. Represents an alkoxy group having 1 to 4 carbon atoms or a cyano group. When R ^1A is a phenyl group, a biphenyl group, a naphthyl group or an anthranyl group, these groups include a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a nitro group. It may be substituted with a substituent selected from the group consisting of groups.
In the formula (2), R ^2A is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or a halogen having 1 to 5 carbon atoms. Represents an alkoxy group, a phenyl group optionally substituted with W, a naphthyl group optionally substituted with W, an anthranyl group optionally substituted with W, a dialkylamino group, a morpholino group, or a cyano group. R ^2A and R ^1A may be bonded to each other to form a 5-membered ring or a 6-membered ring, and the 5-membered ring or 6-membered ring may have one or two arbitrary substituents. It may be bonded to a benzene ring.
In the formula (2), R ^3A represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or a halogen having 1 to 5 carbon atoms. Represents an alkoxy group, a phenyl group optionally substituted with W, a naphthyl group optionally substituted with W, or an anthranyl group optionally substituted with W. W is a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms. Represents a halogenated alkoxy group.

The alkyl group having 1 to 6 carbon atoms represented by R ^1A may be a linear or branched alkyl group, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec- A butyl group, a tert-butyl group, an n-pentyl group, an isoamyl group, an n-hexyl group, or a 2-ethylbutyl group is exemplified.
Examples of the halogenated alkyl group having 1 to 4 carbon atoms represented by R ^1A include a chloromethyl group, a trichloromethyl group, a trifluoromethyl group, and a 2-bromopropyl group.
Examples of the alkoxy group having 1 to 4 carbon atoms represented by R ^1A include a methoxy group or an ethoxy group.
When R ^1A represents a phenyl group, a biphenyl group, a naphthyl group or an anthranyl group, these groups are a halogen atom (for example, a chlorine atom, a bromine atom, an iodine atom, etc.), a hydroxyl group, and a carbon atom having 1 to 4 carbon atoms. Alkyl groups (for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group), alkoxy groups having 1 to 4 carbon atoms (for example, methoxy group, ethoxy group) , N-propoxy group, i-propoxy group, n-butoxy group) and a nitro group may be substituted.

Specific examples of the alkyl group having 1 to 10 carbon atoms represented by R ^2A include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, and s-butyl. Group, t-butyl group, n-amyl group, i-amyl group, s-amyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group and the like. .
Specific examples of the alkoxy group having 1 to 10 carbon atoms represented by R ^2A include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, n-amyloxy group and n-octyl. An oxy group, n-decyloxy group, etc. are mentioned.
Specific examples of the halogenated alkyl group having 1 to 5 carbon atoms represented by R ^2A include trifluoromethyl group, pentafluoroethyl group, perfluoro-n-propyl group, perfluoro-n-butyl group, perfluoro group. Examples include a fluoro-n-amyl group.
Specific examples of the halogenated alkoxy group having 1 to 5 carbon atoms represented by R ^2A include a trifluoromethoxy group, a pentafluoroethoxy group, a perfluoro-n-propoxy group, a perfluoro-n-butoxy group, a perfluoro group. Examples include a fluoro-n-amyloxy group.

Specific examples of the phenyl group optionally substituted by W represented by R ^2A include o-tolyl group, m-tolyl group, p-tolyl group, o-ethylphenyl group, m-ethylphenyl group, p -Ethylphenyl group, p- (n-propyl) phenyl group, p- (i-propyl) phenyl group, p- (n-butyl) phenyl group, p- (i-butyl) phenyl group, p- (s- Butyl) phenyl group, p- (t-butyl) phenyl group, p- (n-amyl) phenyl group, p- (i-amyl) phenyl group, p- (t-amyl) phenyl group, o-methoxyphenyl group , M-methoxyphenyl group, p-methoxyphenyl group, o-ethoxyphenyl group, m-ethoxyphenyl group, p-ethoxyphenyl group, p- (n-propoxy) phenyl group, p- (i-propoxy) phenyl group , P- ( -Butoxy) phenyl group, p- (i-butoxy) phenyl group, p- (s-butoxy) phenyl group, p- (t-butoxy) phenyl group, p- (n-amyloxy) phenyl group, p- (i -Amyloxy) phenyl group, p- (t-amyloxy) phenyl group, p-chlorophenyl group, p-bromophenyl group, p-fluorophenyl group, 2,4-dichlorophenyl group, 2,4-dibromophenyl group, 2, 4-difluorophenyl group, 2,4,6-dichlorophenyl group, 2,4,6-tribromophenyl group, 2,4,6-trifluorophenyl group, pentachlorophenyl group, pentabromophenyl group, pentafluorophenyl group And p-biphenylyl group.

Specific examples of the naphthyl group optionally substituted by W represented by R ^2A include 2-methyl-1-naphthyl group, 3-methyl-1-naphthyl group, 4-methyl-1-naphthyl group, 5 -Methyl-1-naphthyl group, 6-methyl-1-naphthyl group, 7-methyl-1-naphthyl group, 8-methyl-1-naphthyl group, 1-methyl-2-naphthyl group, 3-methyl-2- Naphthyl group, 4-methyl-2-naphthyl group, 5-methyl-2-naphthyl group, 6-methyl-2-naphthyl group, 7-methyl-2-naphthyl group, 8-methyl-2-naphthyl group, etc. It is done.

Specific examples of the anthranyl group optionally substituted with W represented by R ^2A include a 2-methyl-1-anthranyl group, a 3-methyl-1-anthranyl group, a 4-methyl-1-anthranyl group, 5 -Methyl-1-anthranyl group, 6-methyl-1-anthranyl group, 7-methyl-1-anthranyl group, 8-methyl-1-anthranyl group, 9-methyl-1-anthranyl group, 10-methyl-1- Anthranyl group, 1-methyl-2-anthranyl group, 3-methyl-2-anthranyl group, 4-methyl-2-anthranyl group, 5-methyl-2-anthranyl group, 6-methyl-2-anthranyl group, 7- Examples thereof include a methyl-2-anthranyl group, an 8-methyl-2-anthranyl group, a 9-methyl-2-anthranyl group, and a 10-methyl-2-anthranyl group.

^Examples of the dialkylamino group represented by R ^2A include a dimethylamino group, a diethylamino group, a dipropylamino group, a dibutylamino group, and a diphenylamino group.

Specific examples of the alkyl group having 1 to 10 carbon atoms represented by R ^3A include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, and s-butyl. Group, t-butyl group, n-amyl group, i-amyl group, s-amyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group and the like. .
Specific examples of the alkoxy group having 1 to 10 carbon atoms represented by R ^3A include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, n-amyloxy group and n-octyl. An oxy group, n-decyloxy group, etc. are mentioned.
Specific examples of the halogenated alkyl group having 1 to 5 carbon atoms represented by R ^3A include trifluoromethyl group, pentafluoroethyl group, perfluoro-n-propyl group, perfluoro-n-butyl group, perfluoro group. Examples include a fluoro-n-amyl group.
Specific examples of the halogenated alkoxy group having 1 to 5 carbon atoms represented by R ^3A include a trifluoromethoxy group, a pentafluoroethoxy group, a perfluoro-n-propoxy group, a perfluoro-n-butoxy group, a perfluoro group. Examples include a fluoro-n-amyloxy group.

Specific examples of the phenyl group optionally substituted by W represented by R ^3A include o-tolyl group, m-tolyl group, p-tolyl group, o-ethylphenyl group, m-ethylphenyl group, p -Ethylphenyl group, p- (n-propyl) phenyl group, p- (i-propyl) phenyl group, p- (n-butyl) phenyl group, p- (i-butyl) phenyl group, p- (s- Butyl) phenyl group, p- (t-butyl) phenyl group, p- (n-amyl) phenyl group, p- (i-amyl) phenyl group, p- (t-amyl) phenyl group, o-methoxyphenyl group , M-methoxyphenyl group, p-methoxyphenyl group, o-ethoxyphenyl group, m-ethoxyphenyl group, p-ethoxyphenyl group, p- (n-propoxy) phenyl group, p- (i-propoxy) phenyl group , P- ( -Butoxy) phenyl group, p- (i-butoxy) phenyl group, p- (s-butoxy) phenyl group, p- (t-butoxy) phenyl group, p- (n-amyloxy) phenyl group, p- (i -Amyloxy) phenyl group, p- (t-amyloxy) phenyl group, p-chlorophenyl group, p-bromophenyl group, p-fluorophenyl group, 2,4-dichlorophenyl group, 2,4-dibromophenyl group, 2, 4-difluorophenyl group, 2,4,6-dichlorophenyl group, 2,4,6-tribromophenyl group, 2,4,6-trifluorophenyl group, pentachlorophenyl group, pentabromophenyl group, pentafluorophenyl group And p-biphenylyl group.

Specific examples of the naphthyl group optionally substituted by W represented by R ^3A include 2-methyl-1-naphthyl group, 3-methyl-1-naphthyl group, 4-methyl-1-naphthyl group, 5 -Methyl-1-naphthyl group, 6-methyl-1-naphthyl group, 7-methyl-1-naphthyl group, 8-methyl-1-naphthyl group, 1-methyl-2-naphthyl group, 3-methyl-2- Naphthyl group, 4-methyl-2-naphthyl group, 5-methyl-2-naphthyl group, 6-methyl-2-naphthyl group, 7-methyl-2-naphthyl group, 8-methyl-2-naphthyl group, etc. It is done.

Specific examples of the anthranyl group optionally substituted with W represented by R ^3A include a 2-methyl-1-anthranyl group, a 3-methyl-1-anthranyl group, a 4-methyl-1-anthranyl group, 5 -Methyl-1-anthranyl group, 6-methyl-1-anthranyl group, 7-methyl-1-anthranyl group, 8-methyl-1-anthranyl group, 9-methyl-1-anthranyl group, 10-methyl-1- Anthranyl group, 1-methyl-2-anthranyl group, 3-methyl-2-anthranyl group, 4-methyl-2-anthranyl group, 5-methyl-2-anthranyl group, 6-methyl-2-anthranyl group, 7- Examples thereof include a methyl-2-anthranyl group, an 8-methyl-2-anthranyl group, a 9-methyl-2-anthranyl group, and a 10-methyl-2-anthranyl group.

An alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, and a halogenated alkoxy having 1 to 5 carbon atoms represented by W Specific examples include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, and the number of carbon atoms represented by R ^2A or R ^3A. The thing similar to what was mentioned as a specific example of the halogenated alkoxy group of 1-5 is mentioned.

R ^2A and R ^1A may be bonded to each other to form a 5-membered ring or a 6-membered ring.
When R ^2A and R ^1A are bonded to each other to form a 5-membered ring or a 6-membered ring, examples of the 5-membered ring or 6-membered ring include a carbocyclic group and a heterocyclic ring group. It may be a cyclopentane, cyclohexane, cycloheptane, pyrrole, furan, thiophene, imidazole, oxazole, thiazole, pyran, pyridine, pyrazine, morpholine, piperidine or piperazine ring. The 5-membered ring or 6-membered ring may be bonded to an optionally substituted benzene ring, and examples thereof include tetrahydronaphthalene, dihydroanthracene, indene, chroman, fluorene, xanthene, and thiol. Xanthene ring system. The 5-membered or 6-membered ring may contain a carbonyl group, examples of which include cyclohexadienone, naphthalenone and anthrone ring systems.

One of the suitable aspects of the compound represented by said Formula (2) is a compound represented by following formula (2-1). The compound represented by the formula (2-1) is a compound in which R ^2A and R ^1A in the formula (2) are bonded to form a 5-membered ring.

（式（２−１）中、Ｒ^3Aは、式（２）におけるＲ^3Aと同義であり、Ｘは、アルキル基、アルコキシ基又はハロゲン原子を表し、ｔは、０〜３の整数を表し、ｔが２又は３であるとき、複数のＸは同一でも異なっていてもよい。）

(In Formula (2-1), R ^3A has the same meaning as R ^3A in Formula (2), X represents an alkyl group, an alkoxy group, or a halogen atom, t represents an integer of 0 to 3, When t is 2 or 3, the plurality of X may be the same or different.)

The alkyl group represented by X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms.
The alkoxy group represented by X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms.
As the halogen atom represented by X, a chlorine atom or a fluorine atom is preferable.
t is preferably 0 or 1.
In formula (2-1), t is 1, X is a methyl group, the substitution position of X is an ortho position, R ^3A is a linear alkyl group having 1 to 10 carbon atoms, 7,7 A compound having a -dimethyl-2-oxonorbornylmethyl group or a p-toluyl group is particularly preferable.

Specific examples of the oxime sulfonate compound represented by the formula (2-1) include the following compound (i), compound (ii), compound (iii), compound (iv) and the like. One species may be used alone, or two or more species may be used in combination. Compounds (i) to (iv) can be obtained as commercial products.
It can also be used in combination with other types of photoacid generators.

As one of the preferable embodiments of the compound represented by the formula (2),
R ^1A represents an alkyl group having 1 to 4 carbon atoms, a trifluoromethyl group, a phenyl group, a chlorophenyl group, a dichlorophenyl group, a methoxyphenyl group, a 4-biphenyl group, a naphthyl group, or an anthranyl group;
R ^2A represents a cyano group;
R ^3A is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, or W A phenyl group which may be substituted, a naphthyl group which may be substituted with W, or an anthranyl group which may be substituted with W, W represents a halogen atom, a cyano group, a nitro group, or a carbon atom number of 1 Represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or a halogenated alkoxy group having 1 to 5 carbon atoms.

  The compound represented by the formula (2) is also preferably a compound represented by the following formula (2-2).

In formula (2-2), R ^4A represents a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a nitro group, and L represents an integer of 0 to 5. To express. R ^3A is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, or W A phenyl group which may be substituted, a naphthyl group which may be substituted with W, or an anthranyl group which may be substituted with W, W represents a halogen atom, a cyano group, a nitro group, 1 to 1 carbon atoms Represents an alkyl group having 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or a halogenated alkoxy group having 1 to 5 carbon atoms.

R ^3A in the formula (2-2) is methyl group, ethyl group, n-propyl group, n-butyl group, n-octyl group, trifluoromethyl group, pentafluoroethyl group, perfluoro-n-propyl group. Perfluoro-n-butyl group, p-tolyl group, 4-chlorophenyl group or pentafluorophenyl group is preferable, and may be methyl group, ethyl group, n-propyl group, n-butyl group or p-tolyl group. Particularly preferred.
The halogen atom represented by R ^4A is preferably a fluorine atom, a chlorine atom or a bromine atom.
The alkyl group having 1 to 4 carbon atoms represented by R ^4A is preferably a methyl group or an ethyl group.
The alkoxy group having 1 to 4 carbon atoms represented by R ^4A is preferably a methoxy group or an ethoxy group.
As L, 0-2 are preferable, and 0-1 are particularly preferable.

Among the compounds represented by formula (2), as a preferred embodiment of the compound included in the compound represented by formula (2-2), in formula (2), R ^1A is a phenyl group or 4-methoxy. This is an embodiment in which a phenyl group is represented, R ^2A represents a cyano group, and R ^3A represents a methyl group, an ethyl group, an n-propyl group, an n-butyl group, or a 4-tolyl group.

  The compound represented by the formula (1) is also preferably a compound represented by the following formula (1-2).

（式（１−２）中、Ｒ¹はアルキル基、アリール基又はヘテロアリール基を表し、Ｒ²はそれぞれ独立に、水素原子、アルキル基、アリール基又はハロゲン原子を表し、Ｒ⁶はそれぞれ独立に、ハロゲン原子、アルキル基、アルキルオキシ基、スルホン酸基、アミノスルホニル基又はアルコキシスルホニル基を表し、ＸはＯ又はＳを表し、ｎは１又は２を表し、ｍは０〜６の整数を表す。）

(In Formula (1-2), R ¹ represents an alkyl group, an aryl group, or a heteroaryl group, R ² independently represents a hydrogen atom, an alkyl group, an aryl group, or a halogen atom, and R ⁶ represents each independently. Represents a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group, X represents O or S, n represents 1 or 2, and m represents an integer of 0 to 6. Represents.)

  In the photosensitive resin composition, (Component B1) the photoacid generator is preferably used in an amount of 0.1 to 10 parts by weight, based on 100 parts by weight of Component A1, and 0.5 to 10 parts by weight. More preferably it is used.

(Component C1) Solvent The photosensitive resin composition preferably contains (Component C1) a solvent.
The photosensitive resin composition is preferably prepared as a solution prepared by dissolving Component A1 and Component B1 and other optional components described later in (Component C1) solvent.
As the (Component C1) solvent used in the photosensitive resin composition, 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 mono Examples include alkyl ether acetates, esters, ketones, amides, lactones and the like.
Of the above-mentioned solvents, diethylene glycol ethyl methyl ether and / or propylene glycol monomethyl ether acetate are preferable, and propylene glycol monomethyl ether acetate is particularly preferable.
The solvent which can be used for this invention may be used individually by 1 type, or may use 2 types together.

  The content of the (component C1) solvent in the photosensitive resin composition is preferably 50 to 3,000 parts by weight and 100 to 2,000 parts by weight per 100 parts by weight of the component A1. Is more preferable, and it is still more preferable that it is 150-1,500 weight part.

(Component D1) Thermal crosslinking agent The photosensitive resin composition preferably contains (Component D1) a thermal crosslinking agent, if necessary. (Component D1) The heat flow in a baking process can be suppressed by adding a thermal crosslinking agent. In addition, component D1 in this invention shall be things other than component A1, component A2, and component A3.
Preferred examples of the thermal crosslinking agent include a blocked isocyanate crosslinking agent, an alkoxymethyl group-containing crosslinking agent, an epoxy resin having an epoxy group, a (meth) acrylic resin having a carboxy group, and the like.
Among these, a blocked isocyanate crosslinking agent is particularly preferable from the viewpoints of resist sensitivity and storage stability. Moreover, an alkoxymethyl group-containing crosslinking agent can also be suitably used, and preferably contains at least a methylolated melamine compound.

<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.
Among these alkoxymethyl group-containing crosslinking agents, alkoxymethylated melamine, alkoxymethylated benzoguanamine, and alkoxymethylated glycoluril are mentioned as preferred alkoxymethyl group-containing crosslinking agents. From the viewpoint of transparency, alkoxymethylated glycoluril is Particularly preferred.

  These alkoxymethyl group-containing crosslinking agents are available as commercial products, for example, Cymel 300, 301, 303, 370, 325 (manufactured by Mitsui Cyanamid Co., Ltd.), Nicarax MX-750, -270, Nicarak MS. -11, Nicalac MW-30HM, -100LM, -390, (manufactured by Sanwa Chemical Co., Ltd.) and the like can be preferably used. Among these, Nicalac MX-270 and Nicalac MW-100LM are particularly preferable.

  When the alkoxymethyl group-containing crosslinking agent is used in the photosensitive resin composition, the addition amount of the alkoxymethyl group-containing crosslinking agent is 0.05 to 50 parts by weight with respect to 100 parts by weight of the component A1. Is preferably 0.5 to 10 parts by weight, and more preferably 0.5 to 5 parts by weight. By adding in this range, high sensitivity and preferable alkali solubility during development can be obtained.

<Block isocyanate cross-linking agent>
The blocked isocyanate crosslinking agent is not particularly limited as long as it is a compound having a blocked isocyanate group (block isocyanate compound), but is a compound having two or more blocked isocyanate groups in one molecule from the viewpoint of curability. Is preferred.
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 block isocyanate group is a group which can produce | generate an isocyanate group with the heat | fever of 90 to 250 degreeC.
Further, the block isocyanate-based crosslinking agent is not particularly limited in its skeleton, and includes hexamethylene diisocyanate (HDI) skeleton, isophorone diisocyanate (IPDI) skeleton, and a prepolymer type skeleton derived from HDI or IPDI. A compound can be preferably used.

The blocking agent for the isocyanate group in the blocked isocyanate group is not particularly limited, and active methylene compounds such as diester compounds, active hydrogen compounds such as oxime compounds, lactam compounds, and amine compounds can be preferably used. Among these, an active methylene compound is particularly preferable from the viewpoint of reactivity.
Examples of the active methylene compound include diethyl malonate, dimethyl malonate, ethyl acetoacetate, methyl acetoacetate and the like.
Examples of the oxime compound include cyclohexanone oxime, benzophenone oxime, acetoxime, and the like.
Examples of the lactam compound include ε-caprolactam and γ-butyrolactam.
Examples of the amine compound include aniline, diphenylamine, ethyleneimine, and polyethyleneimine.
In addition, the said active hydrogen compound reacts with an isocyanate group as shown in a following formula, and forms a blocked isocyanate group.
R—NCO + HR ′ → R—NH—C (═O) —R ′
(Wherein HR ′ represents an active hydrogen compound, H in HR ′ represents an active hydrogen atom, R represents a moiety other than the isocyanate group in the isocyanate compound, and R ′ represents the active hydrogen compound in the active hydrogen compound) It represents a part other than the active hydrogen atom.)

  These blocked isocyanate crosslinking agents are available as commercial products, for example, Duranate MF-K60X, MF-K60B, MF-B60X, 17B-60P, TPA-B80E, E402-B80B, SBN-70D, K6000 (or more Asahi Kasei Chemicals Co., Ltd.), Death Module BL3272, BL3575 / 1 (above, Sumika Bayer Urethane Co., Ltd.), Urehyper PUR-1804 (DIC Co., Ltd.) and the like can be preferably used. Among these, Duranate MF-K60X, MF-K60B, SBN-70D, and K6000 are particularly preferable.

  When the blocked isocyanate crosslinking agent is used in the photosensitive resin composition, the addition amount of the blocked isocyanate crosslinking agent is preferably 0.1 to 50 parts by weight with respect to 100 parts by weight of component A1. 1 to 20 parts by weight, more preferably 3 to 15 parts by weight. By adding in this range, high sensitivity and preferable alkali solubility during development can be obtained.

(Component E1) Compound having a functional group equivalent of 400 g / eq or more of the total of epoxy group, oxetanyl group, hydroxyl group and carboxy group The photosensitive resin composition has a rectangular profile after baking by suppressing curing shrinkage of the film. In order to obtain it, it is preferable to add a compound having a functional group equivalent total of 400 g / eq or more of the epoxy group, oxetanyl group, hydroxyl group and carboxy group.
Component E1 is preferably a resin having a weight average molecular weight of 1,000 or more.
Specific examples include a copolymer containing a monomer unit containing an epoxy group, an oxetanyl group, a hydroxyl group and / or a carboxy group.
A compound that does not contain any of the above functional groups, such as polymethyl methacrylate (PMMA) homopolymer, can also be added as component E1.
In addition, in this invention, when the component E1 satisfy | fills the definition of the said component D1, it classify | categorizes into both. For example, when the component E1 is an epoxy resin having an epoxy equivalent of 400 g / eq or more, the epoxy resin is the component D1 and the component E1. In addition, component E1 in this invention shall be things other than component A1 and component A2.
Moreover, there is no restriction | limiting in particular as a measuring method of an epoxy equivalent, an oxetanyl equivalent, a hydroxyl group equivalent, and a carboxy group equivalent, A well-known method can be used, for example, titration of content of the said group in a specific amount of compounds etc. It can be calculated by measuring according to For example, it can be measured with reference to the method described in JIS K7236, K0070, etc.

<Epoxy resin>
As the component E1, an epoxy resin is preferably exemplified. By adding an epoxy resin, the heat flow at the time of baking can be suppressed. Further, the epoxy resin preferably has a large epoxy equivalent in order to obtain a rectangular shape or a profile close to a rectangular shape by suppressing curing shrinkage of the crosslinked film. Specifically, 400 g / eq or more is preferable, 400 to 1,000 g / eq is more preferable, and 400 to 600 g / eq is particularly preferable. Within the above range, since the curing shrinkage is small, a rectangular shape or a profile close to a rectangular shape can be obtained, and the allowable range of process conditions during the production of the cured film is large.
In addition, it is preferable that the measuring method of epoxy equivalent conforms to JIS K7236.

As an epoxy resin, what is marketed and what was synthesize | combined arbitrarily can be used. Specific examples of commercially available epoxy resins having an epoxy equivalent of 400 g / eq or more are shown below.
EPICLON 1050, 1055, 3050, 4050, 7050, AM-020-P, AM-040-P, HM-091, HM-101, 1050-70X, 1050-75X, 1055-75X, 1051-75M, 7070-40K HM-091-40AX, 152, 153, 153-60T, 153-60M, 1121N-80M, 1123P-75M, TSR-601, 1650-75MPX, 5500, 5800, 5300-70, 5500-60, EXA-4850 -150, EXA-4850-1000, EXA-4816, EXA-4822 (manufactured by DIC Corporation).

  The addition amount of the epoxy resin is preferably 10 to 50% by weight, particularly preferably 20 to 40% by weight or more based on the total solid content of the photosensitive resin composition. Within the above range, it is easy to obtain a rectangle or a profile close to a rectangle and to form a desired pattern by a development process.

The molecular weight (weight average molecular weight) of the epoxy resin is preferably 500 or more. When the molecular weight is 500 or less, volatilization in the solvent drying step or outflow in the development step can be suppressed, and the effect of adding the epoxy resin can be sufficiently obtained.
An epoxy resin can also be used individually by 1 type, and 2 or more types can also be mixed and used for it.
In addition, the photosensitive resin composition of the present invention preferably contains an alkoxymethyl group-containing crosslinking agent and an epoxy resin having an epoxy equivalent of 400 g / eq or more, from the viewpoint of obtaining a more rectangular profile.

<(Meth) acrylic resin having carboxy group>
As component E1, (meth) acrylic resin which has a carboxy group is mentioned.
As the (meth) acrylic resin having a carboxy group, one having a large carboxy group equivalent is preferable in order to obtain a rectangular profile by suppressing curing shrinkage of the crosslinked film. Specifically, 400 g / eq or more is preferable, 400 to 1,000 g / eq is more preferable, and 400 to 600 g / eq is particularly preferable.
The (meth) acrylic resin having a carboxy group can be obtained by using a known (meth) acrylic monomer, and adjusting the carboxy group equivalent by adjusting the type and amount ratio of the monomer.
As the acrylic monomer, for example, unsaturated monocarboxylic acid, (meth) acrylic acid esters, and crotonic acid esters (meth) acrylamides are preferable.

  The (meth) acrylic resin having a carboxy group is preferably a copolymer of benzyl (meth) acrylate and (meth) acrylic acid.

  The content of component E1 in the photosensitive resin composition is preferably 0.5 to 50 parts by weight and more preferably 1 to 40 parts by weight with respect to 100 parts by weight of component A1. More preferably, it is 5 to 30 parts by weight. Within the above range, it is easy to obtain a rectangle or a profile close to a rectangle.

<Other ingredients>
The said photosensitive resin composition may contain other components other than the said component A1-component E1.
As other components, it is preferable to add (component F1) sensitizer and (component G1) development accelerator from the viewpoint of sensitivity.
Further, the photosensitive resin composition preferably contains (Component H1) an adhesion improver from the viewpoint of substrate adhesion, and preferably contains (Component I1) a basic compound from the viewpoint of liquid storage stability. From the viewpoint of applicability, (Component J1) a surfactant (such as a fluorine-based surfactant or a silicone-based surfactant) is preferably contained.
Further, if necessary, the photosensitive resin composition includes (Component K1) an antioxidant, (Component L1) a plasticizer, (Component M1) a thermal radical generator, (Component N1) a thermal acid generator, ( Component O1) Known additives such as acid proliferators, ultraviolet absorbers, thickeners, and organic or inorganic suspending agents can be added.
In addition, from the viewpoint of obtaining a more rectangular profile, the photosensitive resin composition is an epoxy resin having an epoxy equivalent of 400 g / eq or more, (Component H1) an adhesion improver, (Component I1) a basic compound, and ( Component J1) It preferably contains a surfactant, an alkoxymethyl group-containing crosslinking agent, an epoxy resin having an epoxy equivalent of 400 g / eq or more, (Component H1) an adhesion improver, (Component I1) a basic compound, and ( Component J1) It is particularly preferred to contain a surfactant.
Hereinafter, the other component which the photosensitive resin composition which can be used for this invention can contain is demonstrated.

(Component F1) Sensitizer In the photosensitive resin composition, in combination with the above-mentioned (Component B1) photoacid generator, (Component F1) a sensitizer can be added to promote the decomposition thereof. .
The sensitizer absorbs actinic rays or radiation and enters an excited state. The sensitizer in an excited state comes into contact with the photoacid generator, and effects such as electron transfer, energy transfer, and heat generation occur. Thereby, a photo-acid generator raise | generates a chemical change and decomposes | disassembles and produces | generates an acid.
Examples of preferable sensitizers include compounds belonging to the following compounds and having an absorption wavelength in the 350 nm to 450 nm region.

  Polynuclear aromatics (eg, pyrene, perylene, triphenylene, anthracene), xanthenes (eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), xanthones (eg, xanthone, thioxanthone, dimethylthioxanthone, diethylthioxanthone) ), Cyanines (eg thiacarbocyanine, oxacarbocyanine), merocyanines (eg merocyanine, carbomerocyanine), rhodocyanines, oxonols, thiazines (eg thionine, methylene blue, toluidine blue), acridines ( For example, acridine orange, chloroflavin, acriflavine), acridones (eg, acridone, 10-butyl-2-chloroacridone), anthraquinones (eg, Ntorakinon), squaryliums (e.g., squarylium), styryl compounds, base styryl, coumarins (e.g., 7-diethylamino-4-methylcoumarin). Among these sensitizers, polynuclear aromatics, acridones, coumarins, and base styryls are particularly preferable.

A commercially available sensitizer may be used, or it may be synthesized by a known synthesis method.
The addition amount of the sensitizer is preferably 20 to 300 parts by weight, particularly preferably 30 to 200 parts by weight, with respect to 100 parts by weight of (Component B1) the photoacid generator, from the viewpoint of both sensitivity and transparency.

(Component G1) Development accelerator The photosensitive resin composition preferably contains (Component G1) a development accelerator.
(Component G1) As the development accelerator, any compound having a development acceleration effect can be used, but the compound has at least one structure selected from the group consisting of a carboxy group, a phenolic hydroxyl group, and an alkyleneoxy group. The compound having a carboxy group or a phenolic hydroxyl group is more preferable, and the compound having a phenolic hydroxyl group is most preferable.
The molecular weight of the (component G1) development accelerator is preferably 100 to 2,000, more preferably 150 to 1,500, and particularly preferably 150 to 1,000.

Examples of development accelerators having an alkyleneoxy group include polyethylene glycol, polyethylene glycol monomethyl ether, polyethylene glycol dimethyl ether, polyethylene glycol glyceryl ester, polypropylene glycol glyceryl ester, polypropylene glycol diglyceryl ester, polybutylene glycol, Examples thereof include polyethylene glycol-bisphenol A ether, polypropylene glycol-bisphenol A ether, polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, and compounds described in JP-A-9-222724.
Examples of compounds having a carboxy group include compounds described in JP-A 2000-66406, JP-A 9-6001, JP-A 10-20501, JP-A 11-338150, and the like.
Examples of those having a phenolic hydroxyl group include JP-A No. 2005-346024, JP-A No. 10-133366, JP-A No. 9-194415, JP-A No. 9-222724, JP-A No. 11-171810, Examples thereof include compounds described in JP 2007-121766, JP-A-9-297396, JP-A 2003-43679, and the like. Among these, a phenol compound having 2 to 10 benzene rings is preferable, and a phenol compound having 2 to 5 benzene rings is more preferable. Particularly preferred is a phenolic compound disclosed as a dissolution accelerator in JP-A-10-133366.

(Component G1) The development accelerator may be used alone or in combination of two or more.
The addition amount of (Component G1) development accelerator in the photosensitive resin composition is preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of Component A1 from the viewpoint of sensitivity and residual film ratio. 2 to 20 parts by weight is more preferable, and 0.5 to 10 parts by weight is most preferable.

(Component H1) Adhesion Improving Agent The photosensitive resin composition preferably contains (Component H1) an adhesion improving agent.
(Component H1) adhesion improver that can be used in the photosensitive resin composition is an inorganic material that serves as a substrate, for example, a silicon compound such as silicon, silicon oxide, or silicon nitride, a metal such as gold, copper, or aluminum, and an insulating film. It is a compound that improves the adhesion. Specific examples include silane coupling agents and thiol compounds. The silane coupling agent as the (component H1) adhesion improver used in the present invention is for the purpose of modifying the interface, and any known silane coupling agent can be used without any particular limitation.

Preferred silane coupling agents include, for example, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltriacoxysilane, γ-glycidoxypropylalkyldialkoxysilane, γ- Methacryloxypropyltrialkoxysilane, γ-methacryloxypropylalkyldialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrialkoxysilane, vinyltri An alkoxysilane is mentioned.
Among these, γ-glycidoxypropyltrialkoxysilane and γ-methacryloxypropyltrialkoxysilane are more preferable, and γ-glycidoxypropyltrialkoxysilane is more preferable.

These can be used alone or in combination of two or more. These are effective in improving the adhesion to the substrate and are also effective in adjusting the taper angle with the substrate.
The content of the (component H1) adhesion improver in the photosensitive resin composition is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, with respect to 100 parts by weight of the component A1. preferable.

(Component I1) Basic Compound The photosensitive resin composition preferably contains (Component I1) a basic compound.
(Component I1) The basic compound can be arbitrarily selected from those used in chemically amplified resists. Examples thereof include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, and quaternary ammonium salts of carboxylic acids.

Examples of the aliphatic amine include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine, and dicyclohexylamine. , Dicyclohexylmethylamine and the like.
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, 1,5-diazabicyclo [4.3.0] -5-nonene, 1,8-diazabicyclo [5.3.0] -7 -Undecene and the like.
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.

The basic compound which can be used for this invention may be used individually by 1 type, or may use 2 or more types together.
The content of the (Component I1) basic compound in the photosensitive resin composition is preferably 0.001 to 1 part by weight with respect to 100 parts by weight of Component A1, and preferably 0.002 to 0.001. More preferably, it is 2 parts by weight.

(Component J1) Surfactant (fluorine surfactant, silicone surfactant, etc.)
The photosensitive resin composition preferably contains (Component J1) a surfactant (such as a fluorine-based surfactant or a silicone-based surfactant).
As a surfactant, a copolymer (3) containing the structural unit A and the structural unit B shown below can be given as a preferred example. The weight average molecular weight (Mw) of the copolymer is preferably 1,000 or more and 10,000 or less, and more preferably 1,500 or more and 5,000 or less. The weight average molecular weight is a value in terms of polystyrene measured by gel permeation chromatography (GPC).

In the copolymer (3), R ²¹ and R ²³ each independently represent a hydrogen atom or a methyl group, R ²² represents a linear alkylene group having 1 to 4 carbon atoms, and R ²⁴ represents a hydrogen atom or carbon number. 1 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 weight percentages representing a polymerization ratio, and p is a numerical value of 10% to 80% by weight. Q represents a numerical value of 20% by weight to 90% by weight, r represents an integer of 1 to 18 and n represents an integer of 1 to 10.
L in the structural unit B is preferably an alkylene group represented by the following formula (4).

In the formula (4), R ²⁵ 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 to the coated surface. More preferred is an alkyl group of 3.
The sum of p and q (p + q) is preferably p + q = 100, that is, 100% by weight.

  Specific examples of fluorine surfactants and silicone surfactants include JP-A Nos. 62-36663, 61-226746, 61-226745, and 62-170950. , JP-A-63-34540, JP-A-7-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988, JP-A-2001-330953, etc. An activator can be mentioned and a commercially available surfactant can also be used. Commercially available surfactants that can be used include, for example, F-top EF301, EF303 (Mitsubishi Materials Electronics Kasei Co., Ltd.), Florard FC430, 431 (Sumitomo 3M Co., Ltd.), MegaFuck F171, F173 , F176, F189, R08 (above, manufactured by DIC Corporation), Surflon S-382, SC101, 102, 103, 104, 105, 106 (above, manufactured by Asahi Glass Co., Ltd.), PolyFox series (produced by OMNOVA), etc. Fluorine-based surfactant or silicone-based surfactant. Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicone surfactant.

These surfactants can be used individually by 1 type or in mixture of 2 or more types. Moreover, you may use together a fluorine-type surfactant and a silicone type surfactant.
The addition amount of (component J1) surfactant (fluorine-based surfactant, silicone-based surfactant, etc.) in the photosensitive resin composition is 10 parts by weight or less with respect to 100 parts by weight of component A1. Preferably, it is 0.01 to 10 parts by weight, more preferably 0.01 to 1 part by weight.

(Component K1) Antioxidant The photosensitive resin composition may contain (Component K1) an antioxidant.
(Component K1) As an antioxidant, a well-known antioxidant can be contained. By adding (component K1) antioxidant, coloring of the cured film can be prevented, or the film thickness reduction due to decomposition can be reduced, and the heat-resistant transparency is excellent.
Examples of such antioxidants include phosphorus antioxidants, hydrazides, hindered amine antioxidants, sulfur antioxidants, phenolic antioxidants, ascorbic acids, zinc sulfate, sugars, nitrites, sulfites. Examples thereof include salts, thiosulfates, and hydroxylamine derivatives. Among these, a phenolic antioxidant is particularly preferable from the viewpoint of coloring the cured film and reducing the film thickness. These may be used alone or in combination of two or more.

  As a commercial item of a phenolic antioxidant, ADK STAB AO-60, ADK STAB AO-80 (above, the product made from ADEKA), and Irganox 1098 (made by Ciba Japan Co., Ltd.) are mentioned, for example.

The content of (Component K1) antioxidant is preferably 0.1 to 6% by weight, more preferably 0.2 to 5% by weight, based on the total solid content of the photosensitive resin composition. It is preferably 0.5 to 4% by weight. 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.
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 L1) Plasticizer The photosensitive resin composition may contain (Component L1) a plasticizer.
(Component L1) 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 content of the (component L1) plasticizer in the photosensitive resin composition is preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of the component A1, and preferably 1 to 10 parts by weight. It is more preferable.

(Component M1) Thermal radical generator The photosensitive resin composition may contain (Component M1) a thermal radical generator, such as a compound having at least one ethylenically unsaturated double bond as described above. When an ethylenically unsaturated compound is contained, it is preferable to contain (Component M1) a thermal radical generator.
As the thermal radical generator, a known thermal radical generator can be used.
The thermal radical generator is a compound that generates radicals by heat energy and initiates or accelerates the polymerization reaction of the polymerizable compound. By adding a thermal radical generator, the obtained cured film becomes tougher and heat resistance and solvent resistance may be improved.
Preferred thermal radical generators include aromatic ketones, onium salt compounds, organic peroxides, thio compounds, hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, carbon Examples thereof include compounds having a halogen bond, azo compounds, and bibenzyl compounds.
(Component M1) A thermal radical generator may be used individually by 1 type, and it is also possible to use 2 or more types together.
The content of the (component M1) thermal radical generator in the photosensitive resin composition is preferably 0.01 to 50 parts by weight when the content of the component A1 is 100 parts by weight from the viewpoint of improving film properties. 0.1-20 weight part is more preferable, and it is most preferable that it is 0.5-10 weight part.

(Component N1) Thermal acid generator In the present invention, (Component N1) a thermal acid generator may be used in order to improve film physical properties and the like in low-temperature curing.
The thermal acid generator is a compound that generates an acid by heat, and is usually a compound having a thermal decomposition point in the range of 130 ° C. to 250 ° C., preferably 150 ° C. to 220 ° C., for example, sulfonic acid, It is a compound that generates a low nucleophilic acid such as carboxylic acid or disulfonylimide.
As the generated acid, sulfonic acid, an alkylcarboxylic acid substituted with an electron withdrawing group or an arylcarboxylic acid having a strong pKa of 2 or less, and a disulfonylimide substituted with an electron withdrawing group are also preferable. Examples of the electron withdrawing group include a halogen atom such as a fluorine atom, a haloalkyl group such as a trifluoromethyl group, a nitro group, and a cyano group.

In the present invention, it is also preferable to use a sulfonic acid ester that does not substantially generate an acid by exposure to exposure light and generates an acid by heat.
The fact that acid is not substantially generated by exposure light exposure can be determined by no change in the spectrum by IR and NMR spectrum measurements before and after the exposure of the compound.
The molecular weight of the thermal acid generator is preferably 230 to 1,000, more preferably 230 to 800.

As the sulfonic acid ester usable in the present invention, a commercially available one may be used, or one synthesized by a known method may be used. The sulfonic acid ester can be synthesized, for example, by reacting a sulfonyl chloride or a sulfonic acid anhydride with a corresponding polyhydric alcohol under basic conditions.
The content of the thermal acid generator in the photosensitive resin composition is preferably 0.5 to 20 parts by weight, particularly preferably 1 to 15 parts by weight with respect to 100 parts by weight of the component A1.

(Component O1) Acid Proliferator The photosensitive resin composition can use (Component O1) an acid multiplier for the purpose of improving sensitivity. The acid proliferating agent 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. In such a compound, since one or more acids increase in one reaction, the reaction proceeds at an accelerated rate as the reaction proceeds. However, the generated acid itself induces self-decomposition, and is generated here. The acid strength is preferably 3 or less as an acid dissociation constant, pKa, and particularly preferably 2 or less.
Specific examples of the acid proliferating agent include paragraphs 0203 to 0223 of JP-A-10-1508, paragraphs 0016 to 0055 of JP-A-10-282642, and page 39, line 12 of JP-T 9-512498. Examples of the compounds described in the first to page 47, line 2 are listed.

  Examples of the acid proliferating agent that can be used in the present invention include pKa such as dichloroacetic acid, trichloroacetic acid, methanesulfonic acid, benzenesulfonic acid, trifluoromethanesulfonic acid, and phenylphosphonic acid, which are decomposed by acid generated from the acid generator Examples include compounds that generate 3 or less acids.

  The content of the acid multiplier in the photosensitive resin composition is 10 to 1,000 parts by weight with respect to 100 parts by weight of (Component B1) photoacid generator. From the viewpoint of contrast, it is preferably 20 to 500 parts by weight.

  The photosensitive resin composition of the first embodiment is particularly preferably a chemically amplified positive photosensitive resin composition (chemically amplified positive photosensitive resin composition).

The second embodiment, which is a preferred embodiment of the photosensitive resin composition, includes (Component A2) (a2-1) a monomer unit having a carboxy group or a phenolic hydroxyl group, and (a2-2) an epoxy group and / or an oxetanyl group. It is the photosensitive resin composition containing the polymer which has a monomer unit which has, (Component B2) quinonediazide compound, and (Component C2) solvent.
The photosensitive resin composition of the second embodiment is particularly preferably a positive photosensitive resin composition.

(Component A2) Polymer having monomer unit (a2-1) and monomer unit (a2-2) The photosensitive resin composition comprises (Component A2) (a2-1) a monomer having a carboxy group or a phenolic hydroxyl group. It is preferable to contain a polymer having a unit and (a2-2) a monomer unit having an epoxy group and / or an oxetanyl group.
Component A2 is a polymer having no monomer unit (a1-1) described above.
The monomer unit (a2-1) is preferably a monomer unit having a carboxy group or a phenolic hydroxyl group described in the section of the monomer unit (a1-1).
A monomer unit (a2-2) is synonymous with the above-mentioned monomer unit (a1-2), and its preferable aspect is also the same.
Component A2 may include the monomer unit (a1-3), a monomer unit having a hydroxyl group other than the phenolic hydroxyl group in the monomer unit (a1-4), and a monomer unit (a1-5).

The content of component A2 in the photosensitive resin composition is preferably 20 to 99% by weight, more preferably 40 to 97% by weight, based on the total solid content of the photosensitive resin composition. 60 to 95% by weight is more preferable. When the content is within this range, the pattern formability upon development is good.
In addition, in the said photosensitive resin composition, you may use together resin other than component A2 in the range which does not prevent the effect of this invention. However, the content of the resin other than the component A2 is preferably smaller than the content of the component A2 from the viewpoint of developability.

(Component B2) Quinonediazide compound The photosensitive resin composition preferably contains (Component B2) a quinonediazide compound.
Component B2 is preferably a 1,2-quinonediazide compound.
The quinonediazide compound is a quinonediazide compound having a function of generating a carboxylic acid upon irradiation with radiation such as ultraviolet rays. For example, 1,2-benzoquinonediazidesulfonate, 1,2-naphthoquinonediazidesulfonate, 1,2-benzoate Examples thereof include quinone diazide sulfonic acid amide and 1,2-naphthoquinone diazide sulfonic acid amide.
Further, as the component B2, those described in paragraphs 018 to 024 of JP-A No. 2003-307847 can be used.

(Component C2) Solvent The photosensitive resin composition preferably contains (Component C2) a solvent.
The content of the (component C2) solvent in the photosensitive resin composition is preferably 50 to 3,000 parts by weight, preferably 100 to 2,000 parts by weight per 100 parts by weight of the component A2. Is more preferable, and it is still more preferable that it is 150-1,500 weight part.
Component C2 has the same meaning as Component C1 described above, and the preferred embodiment is also the same.

<Other ingredients>
The photosensitive resin composition in the second embodiment may contain other components other than the components A2 to C2.
Examples of other components include the components D1 to O1, the ultraviolet absorber, the thickener, and the organic or inorganic precipitation inhibitor.

A third embodiment, which is a preferred embodiment of the photosensitive resin composition, includes (Component A3) a polymer having a carboxy group or a phenolic hydroxyl group, (Component B3) a photopolymerization initiator, (Component C3) a solvent, and ( Component D3) is a photosensitive resin composition containing a polymerizable monomer.
The photosensitive resin composition of the third embodiment is particularly preferably a negative photosensitive resin composition.

(Component A3) Polymer having a carboxy group or a phenolic hydroxyl group The photosensitive resin composition preferably contains (Component A3) a polymer having a carboxy group or a phenolic hydroxyl group.
Component A3 is a polymer having no monomer unit (a1-1) described above.
The monomer unit (a3-1) having a carboxy group or a phenolic hydroxyl group in Component A3 is a monomer unit having a carboxy group or a monomer unit having a phenolic hydroxyl group described above in the monomer unit (a1-1). preferable.
Component A3 includes the monomer unit (a1-2), monomer unit (a1-3), monomer unit having a hydroxyl group other than the phenolic hydroxyl group in the monomer unit (a1-4), and monomer unit (a1-5). May be included.

The content of Component A3 in the photosensitive resin composition is preferably 20 to 95% by weight, more preferably 25 to 80% by weight, based on the total solid content of the photosensitive resin composition. 30 to 50% by weight is more preferable. When the content is within this range, the pattern formability upon development is good.
In addition, in the said photosensitive resin composition, you may use resin other than component A3 together in the range which does not prevent the effect of this invention. However, the content of the resin other than the component A3 is preferably smaller than the content of the component A3 from the viewpoint of developability.

(Component B3) Photopolymerization Initiator The photosensitive resin composition preferably contains (Component B3) a photopolymerization initiator.
The photopolymerization initiator can generate radical species capable of initiating polymerization of (Component D3) polymerizable monomer by irradiation with radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray. A compound.
Examples of such photopolymerization generators include light such as oxime ester compounds, imidazole compounds, benzoin compounds, benzophenone compounds, α-diketone compounds, polynuclear quinone compounds, xanthone compounds, diazo compounds, and the like. Preferable examples include radical polymerization initiators.
Component B3 may be used alone or in combination of two or more.
Moreover, as component B3, an oxime ester type compound is preferable.
(Component B3) The content of the photopolymerization initiator is preferably 0.01 to 80 parts by weight and more preferably 1 to 60 parts by weight with respect to 100 parts by weight of the polymerizable monomer.

(Component C3) Solvent The photosensitive resin composition preferably contains (Component C3) a solvent.
The content of the (component C3) solvent in the photosensitive resin composition is preferably 50 to 3,000 parts by weight and 100 to 2,000 parts by weight per 100 parts by weight of the component A3. Is more preferable, and it is still more preferable that it is 150-1,500 weight part.
Component C3 has the same meaning as Component C1 described above, and the preferred embodiment is also the same.

(Component D3) polymerizable monomer,
The photosensitive resin composition preferably contains (Component D3) a polymerizable monomer.
The polymerizable monomer in the present invention is not particularly limited as long as it has a polymerizable ethylenically unsaturated bond, but has two or more polymerizable ethylenically unsaturated bonds (component B3 It is preferably a monomer that can be polymerized by radical species generated when the photopolymerization initiator is irradiated with radiation.
Examples of such polyfunctional monomers include diacrylates or dimethacrylates of alkylene glycols such as ethylene glycol and propylene glycol; diacrylates or dimethacrylates of polyalkylene glycols such as polyethylene glycol and polypropylene glycol; glycerin. , Polyacrylates or polymethacrylates of trihydric or higher polyhydric alcohols such as trimethylolpropane, pentaerythritol, dipentaerythritol, etc., and their dicarboxylic acid modified products; polyester, urethane resin, alkyd resin, silicone resin, spirane resin, etc. Oligoacrylates or oligomethacrylates of: both ends hydroxypoly-1,3-butadiene, both ends hydroxypolyisoprene, both ends hydroxypolycapro Other diacrylates or dimethacrylates of both-terminal hydroxylated polymers such as lactone, can be mentioned tris acryloyloxyethyl phosphate, tris methacryloyloxyethyl phosphate and the like.
Of these polyfunctional monomers, polyacrylates or polymethacrylates of trihydric or higher polyhydric alcohols are preferred, and specifically, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, Pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, succinic acid modified pentaerythritol triacrylate, succinic acid modified Examples include pentaerythritol trimethacrylate and the like, trimethylo Le propane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate is particularly preferred.
The content of Component D3 is preferably 50 to 300 parts by weight, and more preferably 80 to 200 parts by weight with respect to 100 parts by weight of Component A3.

<Other ingredients>
The photosensitive resin composition in the third embodiment may contain components other than the components A3 to D3.
Examples of the other components include the above-described components E1 to O1, ultraviolet absorbers, thickeners, and organic or inorganic precipitation inhibitors.

  Next, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” and “%” are based on weight.

In the following synthesis examples, the following abbreviations represent the following compounds, respectively.
V-65: 2,2′-azobis (2,4-dimethylvaleronitrile)
GMA: Glycidyl methacrylate PGMEA: Propylene glycol monomethyl ether acetate

<Synthesis of Polymer A-1>
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 in the 43-45 ° C./7 mmHg fraction were obtained as a colorless oil.
1-Ethoxyethyl methacrylate (66.41 parts (0.4 molar equivalent)), methacrylic acid (6.9 parts (0.10 molar equivalent)), glycidyl methacrylate (GMA) (49.75 parts ( 0.35 molar equivalent)), 2-hydroxyethyl methacrylate (19.52 parts, (0.15 molar equivalent)) and propylene glycol monomethyl ether acetate (PGMEA) (132.5 parts) in a nitrogen stream Under heating to 70 ° C. While stirring this mixed solution, radical polymerization initiator V-65 (2,2′-azobis (2,4-dimethylvaleronitrile), manufactured by Wako Pure Chemical Industries, Ltd., 12.0 parts) and PGMEA (100 0.0 part) was added dropwise over 3.5 hours. After completion of the dropwise addition, a PGMEA solution of copolymer A-1 (solid content concentration: 40% by weight) was obtained by reacting at 70 ° C. for 4 hours. The weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of the obtained copolymer A-1 was 12,000.

<Synthesis of Polymers A-2 to A-7>
Each monomer used in the synthesis of polymer A-1 was changed to a monomer that forms each monomer unit shown in Table 1, and the amount of the monomer that forms each monomer unit was changed to that shown in Table 1 Respectively synthesized polymers A-2 to A-7 in the same manner as the synthesis of polymer A-1. The amount of radical polymerization initiator V-65 added was adjusted so as to have the molecular weight shown in Table 1.

In addition, the quantity described in Table 1 is a molar ratio, and represents a copolymerization ratio of monomer units derived from each monomer described in the type column. In Table 1, “-” indicates that the monomer unit is not used.
Abbreviations in Table 1 are as follows.
MAEVE: 1-ethoxyethyl methacrylate MATHF: tetrahydrofuran-2-yl methacrylate GMA: glycidyl methacrylate OXE: methacrylic acid (3-ethyloxetane-3-yl) methyl (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
St: styrene DCPM: dicyclopentanyl methacrylate HEMA: 2-hydroxyethyl methacrylate MAA: methacrylic acid HS: p-hydroxystyrene n-BMA: n-butyl methacrylate HS-EVE: the following compound (4- (1-ethoxy ) Ethoxystyrene)
BVGE: Vinyl benzyl glycidyl ether

(Preparation of photosensitive resin composition)
Each component shown in Table 2 below was mixed to obtain a uniform solution, and then filtered using an ethylene filter having a pore size of 0.1 μm to prepare a photosensitive resin composition. Using the obtained photosensitive resin compositions 1 to 9 (compositions 1 to 9), the following evaluations were performed. The evaluation results are shown in Tables 3 and 4.

In addition, the symbol in Table 2 is as follows.
B-1: CGI 1397 (the following compound, manufactured by Ciba Specialty Chemicals)
B-2: α- (p-Toluenesulfonyloxyimino) phenylacetonitrile (the synthesis method is as shown below)
B-3: Oxime sulfonate compound synthesized by the following synthesis method B-4: 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate B-5: 2,3,4,4′- Condensation product of tetrahydroxybenzophenone (1 mol) and 1,2-naphthoquinonediazide-4-sulfonic acid chloride (2 mol) (2,3,4,4′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide- 4-sulfonic acid ester)
B-6: IRGACURE OXE 02 (manufactured by BASF, oxime ester type radical polymerization initiator)
C-1: Propylene glycol monomethyl ether acetate D-1: Nicalac MW-100LM (manufactured by Sanwa Chemical Co., Ltd.)
D-2: Duranate MF-K60X (block isocyanate-based crosslinking agent, active methylene-protected polyfunctional type, manufactured by Asahi Kasei Chemicals Corporation)
D-3: Kayalad DPHA (dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.)
E-1: EPICLON EXA-4816 (manufactured by DIC Corporation, epoxy equivalent: 403 g / eq))
E-2: JER157S65 (Mitsubishi Chemical Corporation, epoxy equivalent: 200 to 220 g / eq)
F-1: 9,10-Dibutoxyanthracene (DBA)
H-1: 3-Glycidoxypropyltrimethoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.)
I-1: 1,5-diazabicyclo [4.3.0] -5-nonene I-2: Triphenylimidazole J-1: Compound W-3 shown below

<Synthesis Method of B-2>
Α- (p-toluenesulfonyloxyimino) phenylacetonitrile was synthesized according to the method described in paragraph 0108 of JP-T-2002-528451.

<Synthesis Method of B-3>
Aluminum chloride (10.6 g) and 2-chloropropionyl chloride (10.1 g) were added to a suspension of 2-naphthol (10 g) and chlorobenzene (30 mL), and the mixture was heated to 40 ° C. for 2 hours. I let you. Under ice-cooling, 4N HCl aqueous solution (60 mL) was added dropwise to the reaction solution, and ethyl acetate (50 mL) was added for liquid separation. Potassium carbonate (19.2 g) was added to the organic layer, reacted at 40 ° C. for 1 hour, 2N HCl aqueous solution (60 mL) was added and separated, and the organic layer was concentrated, and the crystals were diluted with diisopropyl ether (10 mL). The slurry was reslurried, filtered and dried to obtain a ketone compound (6.5 g).
Acetic acid (7.3 g) and 50% aqueous hydroxylamine solution (8.0 g) were added to a suspension of the obtained ketone compound (3.0 g) and methanol (30 mL), and the mixture was heated to reflux. After allowing to cool, water (50 mL) was added, and the precipitated crystals were filtered, washed with cold methanol, and dried to obtain an oxime compound (2.4 g).
The obtained oxime compound (1.8 g) was dissolved in acetone (20 mL), triethylamine (1.5 g) and p-toluenesulfonyl chloride (2.4 g) were added under ice cooling, and the temperature was raised to room temperature. Reacted for hours. Water (50 mL) was added to the reaction solution, and the precipitated crystals were filtered, reslurried with methanol (20 mL), filtered and dried to obtain B-3 (2.3 g).
In addition, the ¹ H-NMR spectrum (300 MHz, CDCl ₃ ) of B-3 is δ = 8.3 (d, 1H), 8.0 (d, 2H), 7.9 (d, 1H), 7. 8 (d, 1H), 7.6 (dd, 1H), 7.4 (dd, 1H) 7.3 (d, 2H), 7.1 (d.1H), 5.6 (q, 1H) , 2.4 (s, 3H), 1.7 (d, 3H).

(1) Evaluation of sensitivity (First aspect, second aspect) (Compositions 1 to 8)
A photosensitive resin composition was slit coated on a silicon wafer having a silicon oxide film, and then prebaked on a hot plate at 90 ° C. for 120 seconds to form a coating film having a thickness of 15 μm.
Next, it exposed through the predetermined | prescribed mask using i line | wire stepper (Canon Co., Ltd. product FPA-3000i5 ^<+> ). Development was carried out with a 2.38% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 90 seconds, followed by rinsing with ultrapure water for 45 seconds. By these operations, the optimum exposure amount (Eopt) when resolving 20 μm line and space at 1: 1 was defined as sensitivity.
1: Eopt is less than 100 mJ / cm ² 2: Eopt is 100 mJ / cm ² or more and less than 300 mJ / cm ² 3: Eopt is 300 mJ / cm ² or more High sensitivity is preferable, and 1 or 2 is a practical range.

(1 ') Evaluation of sensitivity (Third aspect) (Composition 9)
For composition 9, which is a negative photosensitive resin composition, the optimum exposure dose when resolving 20 μm line and space at 1: 1 was measured under the same conditions as in (1) above. The measurement result of the optimum exposure dose was 50 mJ / cm ² .

  It was found that when an oxime sulfonate compound was used as the photoacid generator, the sensitivity was high.

(2) Resin pattern preparation and evaluation The photosensitive resin composition was slit-coated on the silicon wafer which has a silicon oxide film.
Next, the solvent was removed on a hot plate at 90 ° C. for 120 seconds to form a coating film having a thickness of 15 μm.
Next, an optimum exposure exposure was performed through a predetermined mask using an i-line stepper (FPA-3000i5 ⁺ manufactured by Canon Inc.).
Next, the resist film was developed with a 2.38 wt% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 90 seconds and rinsed with ultrapure water for 45 seconds.
Next, the entire pattern was exposed to an entire surface of 300 mJ / cm ² using an ultrahigh pressure mercury lamp.
Next, plasma treatment was performed under any of the following conditions.

<1> Reduced pressure plasma Using a dry etching apparatus “U-621” manufactured by Hitachi High-Technologies Corporation, each setting condition is a gas pressure of 4 Pa, a gas type, and a gas flow rate of CF ₄ gas (tetrafluoromethane) 25 ml. / Min, Ar gas 1,000 ml / min. The source bias was 300 W, the antenna bias was 300 W, the wafer bias was 200 W, and the dry etching processing time was 30 seconds.
Moreover, the film thickness change before and behind plasma processing was measured by newview7300 (made by zygo).

<2> Atmospheric pressure plasma Using the atmospheric pressure plasma apparatus shown in FIG. 1 of JP-A-7-1111195, dry etching treatment was performed. As conditions, the introduced gas was mixed with argon gas as an inert gas, and further propane gas was mixed to stabilize glow discharge. The mixing rate is 2.4 L / min of propane gas with respect to 60 L / min of argon gas. After completely replacing the air with this mixed gas, CF ₄ gas was introduced at a rate of 18 L / min, and a high frequency voltage of 500 V was applied between the upper and lower electrodes. The frequency was 13.5 MHz and the dry etching treatment time was 15 seconds.
Moreover, the film thickness change before and behind plasma processing was measured by newview7300 (made by zygo).

  After the plasma treatment, a resin pattern was produced by heat treatment at 230 ° C. for 60 minutes.

-Evaluation of taper angle-
The cross section of the produced line & space pattern was observed with a scanning electron microscope (SEM), and the taper angle was measured.
Evaluation points 1 to 3 are determined to be practically acceptable levels. An image of the shape is shown in FIG.
1: The taper angle of the line section is 80 ° or more and 90 ° or less 2: The taper angle of the line section is 75 ° or more and less than 80 ° 3: The taper angle of the line section is 70 ° or more and less than 75 ° 4: The taper angle of the line section is 60 ° or more and less than 70 ° 5: The taper angle of the line section is less than 60 °

−Evaluation of rectangularity at the top of the pattern−
Furthermore, the rectangularity of the upper end (14 in FIG. 2 as an example) of the resin pattern produced in the above (2) was evaluated. It is preferable that the upper end is rectangular (rounded). An image of the shape is shown in FIG.
1: The upper end is sharp and square.
2: The upper end is square, but the edge tip is slightly rounded.
3: The upper end was not rounded and rounded.

-Evaluation of rectangularity at the bottom of the pattern-
Furthermore, the rectangularity of the lower end (contact point with the substrate, for example, 16 in FIG. 2) of the resin pattern produced in the above (2) was evaluated. It is preferable that the upper end is rectangular (rounded). An image of the shape is shown in FIG.
1: The lower end is sharp and square. Specifically, the state of Example 1 is mentioned.
2: The lower end is rounded, but the edge tip is slightly rounded.
3: The lower end was not rounded and rounded.

In Examples 1 to 10, the reduced film thickness of the photosensitive resin composition layer before and after the plasma treatment was 50 nm or less.
As shown in Table 4, by performing plasma treatment in the resin pattern manufacturing method, the taper angle, the upper end of the pattern, and the rectangularity of the lower end were improved. The first aspect is particularly preferable from the viewpoint of taper angle and rectangularity.

(3) MEMS fabrication and operation evaluation 1
The photosensitive resin composition 5 is subjected to plasma treatment with reduced-pressure plasma to form a desired pattern, used as a sacrificial layer, and a MEMS shutter device and a 5-inch MEMS shutter device are used according to the method described in JP-T-2008-533510. A display device was manufactured. When the manufactured display device was driven, a clear image was displayed.

(4) MEMS fabrication and operation evaluation 2
In order to fabricate a micromachine described in Japanese Patent Application Laid-Open No. 2000-343463 as a MEMS, the photosensitive resin composition 5 of the present invention is used as a resist film in FIG. A MEMS device was fabricated by a plasma treatment method using plasma, and a performance as a microsensor was evaluated. As a result, good device characteristics were obtained.

(5) Evaluation as etching resist The photosensitive resin composition 5 was slit-coated on the silicon wafer substrate.
Next, the solvent was removed on a hot plate at 90 ° C. for 120 seconds to form a coating film having a thickness of 4.0 μm.
Next, an optimum exposure exposure was performed through a predetermined mask using an i-line stepper (FPA-3000i5 ⁺ manufactured by Canon Inc.).
Next, the film was developed with a 0.4 wt% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 60 seconds and rinsed with ultrapure water for 45 seconds.
Next, the entire pattern was exposed to an entire surface of 300 mJ / cm ² using an ultrahigh pressure mercury lamp.
Dry etching was performed under the reduced pressure plasma conditions.
Next, a heat treatment was performed at 230 ° C. for 20 minutes to obtain a resist pattern.

In order to etch the silicon wafer substrate, dry etching is performed for 90 seconds using a dry etching apparatus (Pintacle 8000) manufactured by PMT, with an etching gas of CF ₄ , a gas flow rate of 75 sccm, a pressure of 2.5 mTorr, and an output of 2500 W. It was.
The resin film part was peeled off by dipping for 10 minutes in a mixed solution (weight ratio = 50: 50) of dimethyl sulfoxide and N, N-dimethylformamide.
Observation with an optical microscope and an electron microscope confirmed that a rectangular pattern faithfully reproducing the mask pattern was obtained on the silicon wafer.

(6) Evaluation as a resist for bump formation <Pattern formation>
After the photosensitive resin composition 5 was applied to a gold sputter substrate using a spin coater, it was heated on a hot plate at 90 ° C. for 5 minutes to form a resin film having a thickness of 25 μm. Next, an optimum exposure exposure was performed using an ultrahigh pressure mercury lamp (HBO manufactured by OSRAM, output 1,000 W) through a pattern mask.
Using an aqueous 2.38 wt% tetramethylammonium hydroxide solution, the film was immersed for 90 seconds at room temperature (25 ° C.) for development, and then washed with running water.
The entire pattern was exposed to an entire surface of 500 mJ / cm ² using an ultrahigh pressure mercury lamp (HBO manufactured by OSRAM, output 1,000 W).
Plasma treatment was performed under the reduced pressure plasma conditions.
Next, a heat treatment was performed at 230 ° C. for 20 minutes to obtain a resin pattern. Hereinafter, the substrate on which the resin pattern is formed is referred to as “patterning substrate (A)”.

<Formation of plated objects>
The patterning substrate (A) was subjected to an ashing treatment (output 100 W, oxygen flow rate 100 ml, treatment time 1 minute) by oxygen plasma as a pretreatment for electroplating to perform a hydrophilic treatment. Next, this substrate is immersed in 1 liter of a cyan gold plating solution (trade name: TEMPEREX 401 manufactured by Nippon Electroplating Engineers Co., Ltd.), and the plating bath temperature is set to 44 ° C. and the current density is set to 0.7 A / dm ² . Then, electrolytic plating was carried out for about 60 minutes to form a bump plating model having a thickness of about 20 μm. Next, it was washed with running water, dried by blowing with nitrogen gas, and then immersed in a mixed solution of dimethyl sulfoxide and N, N-dimethylformamide (weight ratio = 50: 50) at 50 ° C. for 10 minutes. Then, the resin film portion was peeled off, and the conductive layer other than the region where the plated modeled object was formed on the substrate was removed by wet etching to obtain a substrate having the plated modeled object.
Observation with an optical microscope and an electron microscope confirmed that the plating pattern was a faithful reproduction of the mask pattern.

10: Substrate 12: Resin pattern 14: Upper end of resin pattern 16: Lower end of resin pattern θ: Taper angle

Claims (20)

The resin pattern manufacturing method characterized by including at least process (1)-(6) in this order.
(1) Application process for applying photosensitive resin composition on substrate (2) Solvent removal process for removing solvent from applied photosensitive resin composition (3) Activated photosensitive resin composition from which solvent has been removed (4) Development step of developing the exposed photosensitive resin composition with an aqueous developer (5) Ions generated from the surface of the developed photosensitive resin composition and plasmaized gas And / or plasma treatment step for bringing plasma into contact with radicals (6) Heat treatment step for heat treating the plasma-treated photosensitive resin composition   The resin pattern manufacturing method of Claim 1 including the post-exposure process exposed between a process (4) and a process (5) or between a process (5) and a process (6).   The resin pattern manufacturing method of Claim 1 or 2 whose cross-section taper angle of a resin pattern is 70 degrees or more after the heat treatment process of a process (6).   The resin pattern manufacturing method of any one of Claims 1-3 whose film thickness of a resin pattern is 4-100 micrometers after the heat processing process of a process (6).   The resin pattern manufacturing method of any one of Claims 1-4 whose said gas is gas which does not contain oxygen.   The resin pattern manufacturing method according to claim 1, wherein the gas is a gas containing a fluorine compound. The photosensitive resin composition is
(Component A1) (a1-1) a monomer unit having a residue in which a carboxy group or a phenolic hydroxyl group is protected with an acid-decomposable group; and (a1-2) a monomer unit having an epoxy group and / or an oxetanyl group. A polymer having,
(Component B1) a photoacid generator, and
(Component C1) The resin pattern manufacturing method of any one of Claims 1-6 containing a solvent.   The method for producing a resin pattern according to claim 7, wherein the photosensitive resin composition further comprises (Component D1) a thermal crosslinking agent.   The resin pattern manufacturing method of Claim 8 in which component D1 contains a blocked isocyanate compound.   The resin according to any one of claims 7 to 9, wherein Component A1 further comprises a monomer unit having a ring structure (a1-3) in addition to the monomer units (a1-1) and (a1-2). Pattern manufacturing method.   The component A1 according to any one of claims 7 to 10, further comprising (a1-4) a monomer unit having a carboxy group or a hydroxyl group in addition to the monomer units (a1-1) and (a1-2). Resin pattern manufacturing method.   The resin pattern manufacturing method of any one of Claims 7-11 whose content of the monomer unit (a1-1) in the component A is 45 mol% or less with respect to all the monomer units of the component A.   The resin pattern manufacturing method of any one of Claims 1-12 whose said photosensitive resin composition is a chemically amplified positive photosensitive resin composition. The photosensitive resin composition is
(Component A2) (a2-1) a polymer having a monomer unit having a carboxy group or a phenolic hydroxyl group, and (a2-2) a monomer unit having an epoxy group and / or an oxetanyl group,
(Component B2) a quinonediazide compound, and
(Component C2) The resin pattern manufacturing method of any one of Claims 1-6 containing a solvent. The photosensitive resin composition is
(Component A3) a polymer having a carboxy group or a phenolic hydroxyl group,
(Component B3) Photopolymerization initiator,
(Component C3) solvent, and
(Component D3) The resin pattern manufacturing method of any one of Claims 1-6 containing a polymerizable monomer.   The resin pattern manufactured by the resin pattern manufacturing method of any one of Claims 1-15.   The manufacturing method of the MEMS structure which manufactures a structure using the resin pattern of Claim 16 as a sacrifice layer at the time of structure lamination | stacking.   The manufacturing method of the MEMS structure which uses the resin pattern of Claim 16 as a member of a MEMS structure.   A method for manufacturing a semiconductor element, wherein a pattern is formed on a substrate using the resin pattern according to claim 16 as an etching resist.   The plating pattern manufacturing method manufactured by plating using the resin pattern of Claim 16 as a casting_mold | template.

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