JP5616871B2 - Positive photosensitive resin composition, method for producing cured product, method for producing resin pattern, cured product, and optical member - Google Patents

Description

  The present invention relates to a positive photosensitive resin composition, a method for producing a cured product, a method for producing a resin pattern, a cured product, and an optical member.

With the development of solid-state imaging devices and liquid crystal display devices, it has become widely practiced to produce optical members such as microlenses, optical waveguides, and antireflection films using organic materials (resins).
In order to make these optical members have a high refractive index, it has been studied to add particles such as titanium oxide (see Patent Document 1 below).
Moreover, the photosensitive resin composition of patent documents 2-4 is known as a conventional negative photosensitive resin composition.

JP 2006-98985 A JP 2011-127096 A JP 2009-179678 A JP 2008-185683 A

  An object of this invention is to provide the positive photosensitive resin composition which can suppress melt | dissolution of the unexposed part at the time of image development.

The above-described problems of the present invention have been solved by means described in the following <1> or <7> to <10>. It is described below together with <2> to <6> which are preferred embodiments.
<1> (Component A) Inorganic particle, (Component B) Dispersant having an acid group, (Component C) Solvent, (Component D) (a-1) Acid and / or a structural unit having a group capable of leaving by heat And (a-2) a polymer having a structural unit having a crosslinkable group, and (Component E) a photoacid generator, wherein the acid value of Component D is 50 mgKOH / g or less. A positive photosensitive resin composition,
<2> The positive photosensitive resin composition according to <1>, wherein the component A is metal oxide particles,
<3> The positive photosensitive resin composition according to <2>, wherein the component A is titanium oxide particles,
<4> Component B is a graft copolymer having a carboxylic acid group, and the acid value is 100 mgKOH / g or more and 190 mgKOH / g or less, according to any one of the above <1> to <3> Positive photosensitive resin composition,
<5> (Component F) The positive photosensitive resin composition according to any one of <1> to <4>, further including a thermal crosslinking agent,
<6> The positive photosensitive resin composition according to any one of the above <1> to <5>, which is a resin composition for an optical member,
<7> A method for producing a cured product comprising at least steps (a) to (c) in this order,
(A) Coating step of applying the positive photosensitive resin composition according to any one of the above <1> to <6> on a substrate (b) Solvent removal for removing the solvent from the applied resin composition Step (c) Heat treatment step of heat-treating the resin composition from which the solvent has been removed <8> A resin pattern manufacturing method comprising at least steps (1) to (5) in this order,
(1) Application step of applying the positive photosensitive resin composition according to any one of the above <1> to <6> on a substrate (2) Solvent removal for removing the solvent from the applied resin composition Step (3) An exposure step of exposing the resin composition from which the solvent has been removed to a pattern with actinic rays (4) A development step of developing the exposed resin composition with an aqueous developer (5) A developed resin composition Heat treatment step for heat treating <9> The cured product obtained by the method for producing a cured product according to <7> or the resin pattern production method according to <8>,
<10> An optical member obtained by the method for producing a cured product according to <7> or the resin pattern production method according to <8>.

  ADVANTAGE OF THE INVENTION According to this invention, the positive photosensitive resin composition which can suppress melt | dissolution of the unexposed part at the time of image development was able to be provided.

Hereinafter, the resin composition 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.
In the present invention, “(component A) inorganic particles” or the like is also simply referred to as “component A” or the like, and “(a-1) a structural unit having a group capable of leaving by an acid and / or heat” or the like, It is also simply referred to as “structural unit (a-1)”.
Furthermore, in the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what does not have a substituent and what has a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

(Positive photosensitive resin composition)
Hereinafter, each component constituting the positive photosensitive resin composition will be described.
The positive photosensitive resin composition of the present invention (hereinafter also simply referred to as “photosensitive resin composition” or “resin composition”) comprises (Component A) inorganic particles and (Component B) a dispersant having an acid group. (Component C) a solvent, (Component D) (a-1) a polymer having a structural unit having a group capable of leaving by acid and / or heat, and (a-2) a structural unit having a crosslinkable group, and (Component E) A photoacid generator is contained, and the acid value of Component D is 50 mgKOH / g or less.

The positive photosensitive resin composition of the present invention can be suitably used as a positive resist composition.
The positive photosensitive resin composition of the present invention is preferably a resin composition having a property of being cured by heat.
The positive photosensitive resin composition of the present invention is preferably a chemically amplified positive photosensitive resin composition (chemically amplified positive photosensitive resin composition).
The positive photosensitive resin composition of the present invention preferably contains no 1,2-quinonediazide compound as a photoacid generator sensitive to actinic rays. A 1,2-quinonediazide compound generates a carboxy group by a sequential photochemical reaction, but its quantum yield is always 1 or less.
On the other hand, the photoacid generator (component E) used in the present invention acts as a catalyst for the deprotection of the acid-protected acid group generated in response to actinic rays, so one photon The acid produced by the above action contributes to a number of deprotection reactions, and the quantum yield exceeds 1, for example, a large value such as the power of 10, and high sensitivity is obtained as a result of so-called chemical amplification. .

  Furthermore, the positive photosensitive resin composition of the present invention is an optical member such as a microlens, an optical waveguide, an antireflection film, an LED sealing material and an LED chip coating material, or a wiring electrode used for a touch panel. A resin composition for reducing visibility is preferable, and a resin composition for microlenses is more preferable. In addition, the composition for reducing the visibility of the wiring electrode used for the touch panel is a composition for a member that reduces the visibility of the wiring electrode used for the touch panel, that is, makes the wiring electrode difficult to see. Examples thereof include an interlayer insulating film between ITO (indium tin oxide) electrodes, and the positive photosensitive resin composition of the present invention can be suitably used for the application.

In general, when a positive resist is exposed to light, the leaving group of the contained polymer is removed by the action of a photoacid generator, and is dissolved in the developer to form an unexposed portion as a pattern.
When a resin composition containing inorganic particles, a dispersant, and a polymer containing a leaving group and a crosslinking group is used as a positive resist, the solubility in the developer is increased due to the action of the inorganic particles and the dispersant. The present inventors have found that there is a problem that even the exposed portion exhibits solubility in the developer.
As a result of detailed studies, the present inventors have made the positive photosensitive resin composition containing component A to component E, thereby increasing the resistance to the developer in the unexposed areas, and increasing the pattern forming property (during development). It was found that the dissolution inhibition of the unexposed area can be improved.

(Component A) Inorganic Particles The resin composition of the present invention contains inorganic particles for the purpose of adjusting the refractive index and light transmittance.
Component A preferably has a refractive index higher than the refractive index of the resin composition made of a material excluding the particles. Specifically, the refractive index in light having a wavelength of 400 to 750 nm is 1.50. The above particles are more preferable, particles having a refractive index of 1.70 or more are further preferable, and particles having a refractive index of 1.90 or more are particularly preferable.
Here, that the refractive index in light having a wavelength of 400 to 750 nm is 1.50 or more means that the average refractive index in light having a wavelength in the above range is 1.50 or more. It is not necessary that the refractive index of all light having a wavelength is 1.50 or more. The average refractive index is a value obtained by dividing the sum of the measured values of the refractive index for each light having a wavelength in the above range by the number of measurement points.

As such inorganic particles having a high refractive index, inorganic oxide particles are preferable and metal oxide particles are more preferable because of high transparency and light transmittance.
The light-transmitting and high refractive index inorganic oxide particles include Be, Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Gd, Tb, Dy, Yb, Lu, Ti, Zr, Hf, and Nb. , Mo, W, Zn, B, Al, Si, Ge, Sn, Pb, Bi, Te, etc. are preferable, and oxide particles containing titanium oxide, zinc oxide, zirconium oxide, indium / tin oxide, antimony / Tin oxide is more preferred, titanium oxide is more preferred, and titanium dioxide is particularly preferred. Titanium dioxide is particularly preferably a rutile type having a high refractive index. The surface of these inorganic particles can also be treated with an organic material to impart dispersion stability.

  From the viewpoint of the transparency of the resin composition, the average primary particle size of Component A is preferably 1 to 300 nm, particularly preferably 3 to 80 nm. Here, the average primary particle diameter of the particles refers to an arithmetic average obtained by measuring the particle diameter of 200 arbitrary particles with an electron microscope. When the particle shape is not spherical, the longest side is the diameter.

  The content of the inorganic particles in the resin composition of the present invention may be appropriately determined in consideration of the refractive index required for the optical member obtained from the resin composition, light transmittance, and the like. It is preferable to set it as 5 to 80 weight% with respect to the total solid of a composition, and it is more preferable to set it as 10 to 70 weight%.

(Component B) Dispersant having an acid group The resin composition of the present invention contains a dispersant having an acid group.
Examples of the dispersant having an acid group that can be used in the present invention include a polymer dispersant having an acid group (for example, polyamidoamine and salt thereof, polycarboxylic acid and salt thereof, high molecular weight unsaturated acid having an acid group). Ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth) acrylic copolymer, naphthalenesulfonic acid formalin condensate), polyoxyethylene alkyl phosphate ester, polyoxyethylene alkylamine, alkanolamine And pigment derivatives.
The polymer dispersant can be further classified into a linear polymer, a terminal-modified polymer, a graft polymer, and a block polymer from the structure thereof. The polymer dispersant preferably has a weight average molecular weight of 1,000 or more.
Among these, the dispersant having an acid group that can be used in the present invention is preferably a polymer dispersant, and more preferably a graft type polymer dispersant.
The dispersing agent which has an acid group may be used individually by 1 type, and may be used in combination of 2 or more type.

Component B is a dispersant having an acid group. By having an acid group, it is presumed to act as an adsorbing group for the inorganic particles, and the dispersibility of the inorganic particles is excellent.
Examples of the acid group include a carboxylic acid group (carboxy group), a sulfonic acid group, a phosphoric acid group, a phenolic hydroxyl group, and the like, from the viewpoints of adsorption power and dispersibility to inorganic particles, a carboxylic acid group, a sulfonic acid group, and It is preferably at least one selected from the group consisting of phosphoric acid groups, and carboxylic acid groups are particularly preferable. The acid groups in the dispersant may have one of these alone or in combination of two or more.
Moreover, the dispersant having an acid group that can be used in the present invention is preferably a graft copolymer having an acid group, and more preferably a graft copolymer having a carboxylic acid group.
Furthermore, the dispersant having an acid group that can be used in the present invention is preferably a graft copolymer having a structural unit represented by any one of formulas (1) to (4).

（式（１）〜式（４）において、Ｘ¹、Ｘ²、Ｘ³、Ｘ⁴及びＸ⁵はそれぞれ独立に、水素原子又は１価の有機基を表し、Ｗ¹、Ｗ²、Ｗ³及びＷ⁴はそれぞれ独立に、酸素原子又はＮＨを表し、Ｒはそれぞれ独立に、水素原子又は１価の有機基を表し、Ｒ’はそれぞれ独立に、分岐又は直鎖アルキレン基を表し、Ｙ¹、Ｙ²、Ｙ³及びＹ⁴はそれぞれ独立に、２価の連結基を表し、Ｚ¹、Ｚ²、Ｚ³及びＺ⁴はそれぞれ独立に、水素原子又は１価の有機基を表し、ｎ、ｍ、ｐ及びｑはそれぞれ独立に、１〜５００の整数であり、ｊ及びｋはそれぞれ独立に、２〜８の整数である。）

(In Formula (1)-Formula (4), X < ¹ >, X < ² >, X < ³ >, X < ⁴ > and X < ⁵ > represent a hydrogen atom or a monovalent organic group each independently, W < ¹ >, W < ² >, W < ³ >. And W ⁴ each independently represents an oxygen atom or NH, each R independently represents a hydrogen atom or a monovalent organic group, each R ′ independently represents a branched or straight-chain alkylene group, Y ¹ , Y ² , Y ³ and Y ⁴ each independently represents a divalent linking group, Z ¹ , Z ² , Z ³ and Z ⁴ each independently represents a hydrogen atom or a monovalent organic group, n , M, p and q are each independently an integer of 1 to 500, and j and k are each independently an integer of 2 to 8.)

In the formulas (1) to (4), X ¹ , X ² , X ³ , X ⁴ and X ⁵ each independently represent a hydrogen atom or a monovalent organic group. An atom or an alkyl group having 1 to 12 carbon atoms is preferable, a hydrogen atom or a methyl group is more preferable, and a methyl group is particularly preferable.
In the formulas (1) to (4), W ¹ , W ² , W ³ and W ⁴ each independently represent an oxygen atom or NH, and particularly preferably an oxygen atom.

In formula (3), R ′ each independently represents a branched or straight chain alkylene group (the number of carbon atoms is preferably 1-10, more preferably 2 or 3), and from the viewpoint of dispersion stability. , A group represented by —CH ₂ —CH (CH ₃ ) — or a group represented by —CH (CH ₃ ) —CH ₂ — is preferable.
In addition, as R ′ in the formula (3), two or more types of R ′ having different structures may be mixed in one component B and used.

In the formulas (1) to (4), Y ¹ , Y ² , Y ³ and Y ⁴ are each independently a divalent linking group and are not particularly limited in structure. Specific examples include the following (Y-1) to (Y-21) linking groups. In the following structure, A means a bond to the left terminal group of Y ¹ , Y ² , Y ³ or Y ⁴ in formula (1) to formula (4), and B represents formula (1) to formula (4). Means a bond to the right terminal group of Y ¹ , Y ² , Y ³ or Y ⁴ . Of the structures shown below, (Y-2) and (Y-13) are more preferable from the viewpoint of ease of synthesis.

In the formulas (1) to (4), Z ¹ , Z ² , Z ³ and Z ⁴ are each independently a hydrogen atom or a monovalent substituent, and the structure of the substituent is not particularly limited. Examples thereof include an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group, and an amino group. Among these, particularly from the viewpoint of improving dispersibility, Z ¹ and Z ² are each independently preferably an alkyl group having 5 to 24 carbon atoms, a branched alkyl group having 5 to 24 carbon atoms or a cyclic group having 5 to 24 carbon atoms. An alkyl group is more preferred. Z ³ is preferably a hydroxyl group, an alkoxy group or an aryloxy group, and more preferably a hydroxyl group. Z ⁴ is preferably a hydrogen atom, a hydroxyl group or an alkoxy group, more preferably a hydrogen atom.
In the formulas (1) to (4), n, m, p and q are each independently an integer of 1 to 500, preferably an integer of 3 to 500, and an integer of 5 to 50. Is more preferable, and an integer of 8 to 30 is even more preferable.
In Formula (1) and Formula (2), j and k each independently represent an integer of 2 to 8, and from the viewpoint of dispersion stability, an integer of 4 to 6 is preferable and 5 is most preferable.

In formula (4), R represents a hydrogen atom or a monovalent organic group and is not particularly limited in terms of structure, but is preferably a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, and preferably a hydrogen atom, an alkyl group It is more preferable that When R is an alkyl group, the alkyl group is preferably a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 5 to 20 carbon atoms, A linear alkyl group having 1 to 20 carbon atoms is more preferable, and a linear alkyl group having 1 to 6 carbon atoms is particularly preferable.
Moreover, as R in Formula (4), two or more types of R having different structures may be contained in one component B.

  The structural unit represented by the formula (1) is more preferably a structural unit represented by the following formula (1A) or formula (2A) from the viewpoint of dispersion stability.

Wherein (1A), X ^1, Y ^1, Z ¹ and n are as defined X ^1, Y ^1, Z ¹ and n in Formula (1), and preferred ranges are also the same.
Wherein (2A), X ^2, Y ^2, Z ² and m are as defined X ^2, Y ^2, Z ² and m in the formula (2), and preferred ranges are also the same.

Content of the structural unit represented by any one of Formula (1) to Formula (4) in Component B (including multiple types of structural units represented by any one of Formula (1) to Formula (4)) The total content) is preferably in the range of 10 to 90% by weight, more preferably in the range of 30 to 70% by weight, based on the total weight of component B. Within this range, the dispersibility of the inorganic particles is excellent, and the developability when a photosensitive resin composition is obtained is improved.
Further, the resin composition of the present invention may contain component B alone or may contain component B having two or more different structures.

  Component B preferably has a structural unit represented by any one of formulas (1) to (3) among the structural units represented by any of formulas (1) to (4). It is more preferable to have a structural unit represented by any one of formula (1) or formula (2), and it is even more preferable to have a structural unit represented by formula (1).

Component B is more preferably a graft copolymer having at least a structural unit represented by any one of formulas (1) to (4) and a structural unit having an acid group. ) To a formula (4), and a graft copolymer having at least a structural unit having a carboxylic acid group is more preferable.
Among these, component B is particularly preferably a graft copolymer having at least a structural unit represented by any one of formulas (1) to (4) and a structural unit having a phthalic acid monoester structure.

The acid value of Component B is preferably in the range of 5.0 mgKOH / g to 200 mgKOH / g, more preferably in the range of 100 mgKOH / g to 190 mgKOH / g, more preferably 120 mgKOH / g to 190 mgKOH / g. Is more preferable, and a range of 140 mgKOH / g or more and 180 mgKOH / g or less is particularly preferable. It is excellent in the dispersibility of an inorganic particle as it is the said range, and melt | dissolution of the unexposed part at the time of image development can fully be suppressed.
The method for measuring the acid value of Component B is not particularly limited and can be measured by a known method, but can be suitably measured by the same method as the method for measuring the acid value of Component D described later.
Moreover, the acid value of component B can be calculated from the average content of acid groups in component B, for example. Moreover, the component B which has a desired acid value can be obtained by changing content of the structural unit containing the acid group which comprises the component B. FIG.

  The weight average molecular weight of Component B is preferably 10,000 or more and 300,000 or less, more preferably 15,000 or more and 200,000 or less, from the viewpoint of pattern peeling inhibition during development and developability. More preferably, it is 20,000 or more and 100,000 or less, and particularly preferably 25,000 or more and 50,000 or less. In addition, the weight average molecular weight of resin can be measured by GPC (gel permeation chromatography), for example.

  Specific examples of component B include B-1 and B-2 shown below, and B-1 is particularly preferable. In the following formulae, x and y represent a weight ratio, preferably x: y = 40: 60 to 95: 5, and more preferably 70:30 to 90:10.

  The content of Component B in the resin composition of the present invention is preferably 50 to 3,000 parts by weight, more preferably 100 to 2,000 parts by weight per 100 parts by weight of Component A. 150 to 1,500 parts by weight is even more preferable.

(Component C) Solvent The resin composition of the present invention contains (Component C) a solvent.
The resin composition of the present invention is preferably prepared as a solution in which component A and component B and other optional components described below are dissolved or dispersed in (component C) solvent.
As the (Component C) solvent used in the resin composition of the present invention, known solvents can be used, such as ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol. Monoalkyl ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol 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 or more types together.

  The content of the (component C) solvent in the resin composition of the present invention 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 D. Is more preferable, and it is still more preferable that it is 150-1,500 weight part.

(Component D) (a-1) Polymer having a structural unit having a group capable of leaving by acid and / or heat and (a-2) a structural unit having a crosslinking group Positive photosensitive resin composition of the present invention (Component D) (a-1) a structural unit having a group capable of leaving by acid and / or heat (also simply referred to as “leaving group”) and (a-2) a structural unit having a bridging group, A polymer having
The acid value of Component D is 50 mgKOH / g or less, preferably 45 mgKOH / g or less, more preferably 35 mgKOH / g or less, still more preferably 10 mgKOH / g or less, and further preferably 3 mgKOH / g or less. g or less is particularly preferable, and 1 mgKOH / g or less is most preferable. Within the above range, dissolution of the unexposed portion during development can be suppressed. On the other hand, when the acid value of component D exceeds 50 mgKOH / g, dissolution of the unexposed area during development occurs greatly, resulting in deterioration of the pattern shape.
The acid value of component D in the positive photosensitive resin composition of the present invention is an acid value in a state where the structural unit (a-1) having a leaving group is present. For example, when the structural unit (a-1) is a structural unit having a residue in which a carboxy group is protected with an acid-decomposable group, the acid value of the component D after the leaving group is removed is eliminated. Needless to say, it is higher than the previous one.
There is no restriction | limiting in particular as a measuring method of an acid value, Although a well-known method can be used, It is preferable to measure with the following method.
The acid value measurement method in the present invention is not particularly limited and can be appropriately selected from known methods. Examples thereof include titration methods, and the acid value is measured by titration with potassium hydroxide. The method of doing is mentioned preferably.

Component D is preferably a polymer having no sulfur atom from the viewpoint of process suitability in the field of solid-state imaging devices and liquid crystal display devices.
Component D preferably has (a-3) a structural unit having an alkali-soluble group in addition to the structural units (a-1) and (a-2), and (a-3) an alkali-soluble group. And (a-4) a structural unit having an aromatic ring is more preferable. As the alkali-soluble group, a carboxylic acid group (carboxy group) is preferable.
Component D may contain a structural unit (a-5) other than the monomer units (a-1) to (a-4).
The “structural unit” in the present invention includes not only a monomer unit formed from one monomer molecule, but also a structural unit obtained by modifying a monomer unit formed from one monomer molecule by a polymer reaction or the like.

The weight average molecular weight (Mw) of Component D is preferably 3,000 or more, more preferably 5,000 or more, still more preferably 10,000 or more, and 1,000,000. Or less, more preferably 80,000 or less, and still more preferably 60,000 or less. In the above range, good resolution can be obtained.
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 D 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. Component D 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, “structural unit derived from (meth) acrylic acid or its ester” is also referred to as “acrylic structural unit”. (Meth) acrylic acid is a generic term for methacrylic acid and acrylic acid.
Hereinafter, each structural unit such as the structural unit (a-1) and the structural unit (a-2) will be described.

(A-1) Structural unit having a group capable of leaving by acid and / or heat Component D has at least a structural unit having (a-1) a group capable of leaving by acid and / or heat.
The group leaving by acid and / or heat may be a group leaving by acid, a group leaving by heat, or a group leaving by acid and heat, It is preferably at least a group capable of leaving by an acid, that is, a group leaving by an acid or a group leaving by an acid and heat.
Examples of the group capable of leaving at least by an acid include a residue protected with an acid-decomposable group.
From the viewpoint of sensitivity and resolution, the structural unit (a-1) is a structural unit (a-1-1) having a residue in which a carboxy group or a phenolic hydroxyl group is protected with an acid-decomposable group. preferable.
Component D is a resin that is insoluble in alkali when it contains the structural unit (a-1-1), and becomes alkali-soluble when the acid-decomposable group in the structural unit (a-1-1) is decomposed. Preferably there is.
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.

[Structural unit (a-1-1) having a residue in which a carboxy group or a phenolic hydroxyl group is protected with an acid-decomposable group]
Component D preferably has a structural unit (a-1-1) having a residue in which a carboxy group or a phenolic hydroxyl group is protected with an acid-decomposable group.
When component D has the structural unit (a-1-1), a highly sensitive resin composition can be obtained. A structural unit having a residue in which a carboxy group is protected with an acid-decomposable group is characterized by faster development than a structural unit having a residue in which a phenolic hydroxyl group is protected with an acid-decomposable group. Therefore, when it is desired to develop quickly, a structural unit having a residue in which a carboxy group is protected with an acid-decomposable group is preferable. Conversely, when it is desired to delay development, it is preferable to use a structural unit having a residue in which a phenolic hydroxyl group is protected with an acid-decomposable group.
The acid-decomposable group is particularly preferably a 1-ethoxyethyl group or a tetrahydrofuranyl group, and most preferably a tetrahydrofuranyl group.

[Structural unit (a-1-2) having a residue in which a carboxy group is protected with an acid-decomposable group]
-Structural unit having a carboxy group-
As the structural unit having a carboxy group, for example, a structural unit derived from an unsaturated carboxylic acid having at least one carboxy group in the molecule, such as an unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, or unsaturated tricarboxylic acid. Is mentioned.
Examples of the unsaturated carboxylic acid used for obtaining the structural 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, it is preferable to use acrylic acid, methacrylic acid, or an anhydride of an unsaturated polyvalent carboxylic acid in order to form a structural unit having a carboxy group. More preferably, it is used.
The structural unit which has a carboxy group may be comprised individually by 1 type, and may be comprised by 2 or more types.

The structural unit having a carboxy group may be a structural unit obtained by reacting a monomer unit having a hydroxyl group with an acid anhydride.
As the acid anhydride, known ones can be used. Specific examples include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and chlorendic anhydride. 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.

-Structural unit (a-1-2) having a residue in which a carboxy group is protected with an acid-decomposable group-
The structural unit (a-1-2) having a residue in which a carboxy group is protected with an acid-decomposable group is preferably an acid-decomposable structure described in detail below. A structural 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, an acetal functional group such as a tetrahydropyranyl group as a group that is relatively easily decomposed by an acid, a t-butyl ester group, or a t-butyl carbonate as a group that is relatively hardly decomposed by an acid. T-Butyl functional groups such as groups are known and can be used.
Further, such acetal functional group, t-butyl functional group, and the following ketal functional group are functional groups that can be detached even by heat.
Among these acid-decomposable groups, a structural unit having a residue in which a carboxy group is protected with an acetal or a residue in which a carboxy group is protected with a ketal is preferable from the viewpoint of sensitivity and resolution. Furthermore, among the acid-decomposable groups, the carboxy group is more preferably 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す。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, and 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 and R ² each independently represents a hydrogen atom or an alkyl group, R ³ represents an alkyl group, and the alkyl group is linear, branched, or cyclic. But you can. 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.
The aralkyl group is preferably an aralkyl group having 7 to 32 carbon atoms, and more preferably an aralkyl group having 7 to 20 carbon atoms. Specific examples include a benzyl group, an α-methylbenzyl group, a phenethyl group, and a naphthylmethyl group.
As said alkoxy group, a C1-C6 alkoxy group is preferable, a C1-C4 alkoxy group is more preferable, and a methoxy group or an ethoxy group is still more preferable.
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 when it is a branched alkyl group, it may have a C3-C12 cycloalkyl group as a substituent.
These substituents may be further substituted with the above substituents.

In 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, and more preferably has 6 to 10 carbon atoms. 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 preferable.
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 structural unit having the 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 structural unit (a-1-2) having a residue in which a carboxy group is protected with an acid-decomposable group include the following structural units. R represents a hydrogen atom or a methyl group.

[Structural unit (a-1-3) having a residue in which a phenolic hydroxyl group is protected with an acid-decomposable group]
-Structural unit having phenolic hydroxyl group-
Examples of the structural unit having a phenolic hydroxyl group include a hydroxystyrene monomer unit and a structural unit in a novolac resin. Among the structural units having a phenolic hydroxyl group, the structural 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;

-Structural unit having a residue in which a phenolic hydroxyl group is protected with an acid-decomposable group-
The structural unit having a residue in which a phenolic hydroxyl group is protected by an acid-decomposable group is a residue in which the phenolic hydroxyl group of the structural unit having a phenolic hydroxyl group is protected by an acid-decomposable group described in detail below. It is a structural unit.
As the acid-decomposable group, a known group can be used as described above, and is not particularly limited. Among acid-decomposable groups, it is a structural unit having a residue in which a phenolic hydroxyl group is protected with an acetal, or a residue in which a phenolic hydroxyl group is protected with a ketal, particularly sensitivity and storage stability of a resin composition. From the viewpoint of 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 structural 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, a hydroxystyrene Protected tetrahydropyranyl, 1-alkoxyalkyl protected α-methylhydroxystyrene, tetrahydropyranyl protected α-methyl-hydroxystyrene, 1-alkoxyalkyl protected 4-hydroxyphenyl methacrylate, 4-hydroxyphenyl methacrylate And the tetrahydropyranyl protected form.

  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 (a-1-3) include the following structural units, but the present invention is not limited thereto. R in the structural units below represents a hydrogen atom or a methyl group.

The structural unit (a-1) is preferably a monomer unit having a residue in which a carboxy group or a phenolic hydroxyl group is protected with a 1-ethoxyethyl group or a tetrahydrofuranyl group.
The content of the monomer unit constituting the structural unit (a-1) in Component D is preferably from 3 to 70 mol%, more preferably from 10 to 65 mol%, based on the total monomer units of Component D, from the viewpoint of sensitivity. 20-60 mol% is still more preferable, and 35-45 mol% is especially preferable.

(A-2) Structural unit having a crosslinking group Component D has at least a structural unit (a-2) having a crosslinking group.
The crosslinking group is not particularly limited as long as it is a group that causes a curing reaction by heat treatment. As a preferred embodiment of the structural unit having a crosslinking group, there is a structural unit containing at least one selected from the group consisting of a structural unit having an epoxy group and / or an oxetanyl group and a structural unit having an ethylenically unsaturated group. Can be mentioned. In more detail, the following are mentioned.
From the viewpoint of storage stability and cured film properties, the structural unit (a-2) is preferably a structural unit (a-2-1) having an epoxy group and / or an oxetanyl group.

<Constitutional Unit Having Epoxy Group and / or Oxetanyl Group (a-2-1)>
Component D preferably has a structural unit (a-2-1) having an epoxy group and / or an oxetanyl group. Component D may have both a structural unit having an epoxy group and a structural unit having an oxetanyl group. Moreover, it is preferable that the component D has the structural unit which has oxetanyl group from a transparent viewpoint of hardened | cured material.
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 structural unit (a-2-1) may have at least one epoxy group or oxetanyl group in one monomer unit, and one or more epoxy groups and one or more oxetanyl groups, two or more The epoxy group 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 the epoxy group and / or oxetanyl group. Are preferably 1 or 2 in total, and more preferably 1 epoxy group or oxetanyl group.

Specific examples of the radical polymerizable monomer used to form the structural 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 according to paragraphs 0031 to 0035 of Japanese Patent No. 4168443 Examples include compounds containing an epoxy skeleton That.
Examples of the radical polymerizable monomer used for forming the structural 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.

Examples of the radical polymerizable monomer used for forming the structural unit (a-2-1) are preferably a monomer containing a methacrylic ester structure and a monomer containing an acrylate ester structure.
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 include (meth) acrylic acid esters having an oxetanyl group described in paragraphs 0011 to 0016 of the publication.
From the viewpoint of heat-resistant transparency, particularly preferred is a structural unit derived from either acrylic acid (3-ethyloxetane-3-yl) methyl or methacrylic acid (3-ethyloxetane-3-yl) methyl. It is.
These structural units (a-2-1) can be used individually by 1 type or in combination of 2 or more types.

  Preferable specific examples of the structural unit (a-2-1) include the following structural units.

<Constitutional unit having ethylenically unsaturated group (a-2-2)>
As one of the structural units (a-2) having a crosslinking group, there may be mentioned a structural unit (a-2-2) having an ethylenically unsaturated group.
The structural unit (a-2-2) having an ethylenically unsaturated group is preferably a structural unit having an ethylenically unsaturated group in the side chain, having an ethylenically unsaturated group at the terminal, and having 3 to 3 carbon atoms. A structural unit having 16 side chains is more preferred, and a structural unit having a side chain represented by formula (a2-2-2) is more preferred.

（式（ａ２−２−２）中、Ｒ¹は炭素数１〜１３の二価の連結基を表し、Ｒ²及びＲ³はそれぞれ独立に、水素原子又はメチル基を表す。）

(In formula (a2-2-2), R ¹ represents a divalent linking group having 1 to 13 carbon atoms, and R ² and R ³ each independently represent a hydrogen atom or a methyl group.)

R ¹ may be a divalent linking group having 1 to 13 carbon atoms, and preferably includes an alkenyl group, a cycloalkenyl group, an arylene group, or a group obtained by combining these, and an ester bond, an ether bond, A bond such as an amide bond or a urethane bond may be included. The divalent linking group may have a substituent such as a hydroxy group or a carboxy group at an arbitrary position.

  The content of the monomer units constituting the structural unit (a-2) in Component D is preferably 5 to 60 mol%, more preferably 10 to 55 mol%, more preferably 30 to 50 mol, based on all monomer units of Component D. % Is particularly preferred. By containing the structural unit (a-2) at the above ratio, the physical properties of the cured film are improved.

(A-3) Structural Unit Having Alkali-Soluble Group Component D may have a structural unit (a-3) having an alkali-soluble group.
(A-3) The structural unit having an alkali-soluble group has a function of imparting alkali solubility to Component D. However, the content of the structural unit (a-3) in Component D is limited to an amount such that the acid value of Component D is 50 mgKOH / g or less. When component D has structural unit (a-3), component D is easily dissolved in an alkaline solution (developer) during development, and component D containing structural unit (a-3) can be easily developed with a developer. . In addition, the alkali-soluble group-containing monomer is bonded with an epoxy group or an oxetanyl group (for example, a group derived from the structural unit (a-2-1)) in the component D molecule by crosslinking using a crosslinking agent. It hardens | cures by reaction and gives hardness to the obtained hardened | cured material.
The alkali-soluble group in the structural unit (a-3) having an alkali-soluble group may be a group usually used in the resist field, and examples thereof include a carboxy group and a phenolic hydroxyl group. Representative examples of the structural unit (a-3) having an alkali-soluble group include, but are not limited to, an unsaturated carboxylic acid or an acid anhydride thereof, hydroxystyrene or a derivative thereof.
As the structural unit (a-3), a structural unit having the carboxy group or a structural unit having a phenolic hydroxyl group can be suitably used. Among these, unsaturated carboxylic acid or its acid anhydride is particularly preferable.

  Examples of unsaturated carboxylic acids or acid anhydrides thereof include α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, and acid anhydrides thereof (maleic anhydride, An itaconic anhydride, etc.). Among these, acrylic acid and methacrylic acid are particularly preferable. The structural unit (a-3) having an alkali-soluble group can be used alone or in combination of two or more.

  When the component D has the structural unit (a-3), the content of the monomer unit constituting the structural unit (a-3) in the component D is 0.1 to 14 mol% with respect to all the monomer units of the component D. Is preferable, 0.1-12 mol% is still more preferable, and 0.1-5 mol% is especially preferable. By incorporating the structural unit (a-3) at the above ratio, developability is improved.

(A-4) Structural Unit Having Aromatic Ring Component D is a structural unit other than the structural units (a-1) to (a-3) from the viewpoint of refractive index (a- It is preferable to have 4).
Examples of the monomer that forms the structural unit (a-4) include styrenes and (meth) acrylic acid esters having an aromatic ring.
Among these, a structural unit derived from styrene and a structural unit derived from benzyl (meth) acrylate are preferable, and a structural unit derived from benzyl methacrylate is more preferable.

  When Component D has the structural unit (a-4), the content of the monomer units constituting the structural unit (a-4) in Component D is preferably 5 to 35 mol% with respect to all the monomer units of Component D. 10-30 mol% is more preferable. By including the structural unit (a-4) at the above ratio, the physical properties of the cured film are improved.

(A-5) Other structural unit Component D has structural units (a-5) other than the structural units (a-1) to (a-4) as long as the effects of the present invention are not hindered. May be.
Examples of the radical polymerizable monomer used for forming the structural unit (a-5) include the compounds described in paragraphs 0021 to 0024 of JP-A No. 2004-264623 (provided that the above-described units are not included). The monomers that form the structural units (a-1) to (a-4) are excluded.
The radically polymerizable monomer used to form the structural unit (a-5) includes an alicyclic structure such as dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, and cyclohexyl acrylate. (Meth) acrylic acid esters, methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, styrene and the like can be preferably exemplified.
Of these, 2-hydroxyethyl (meth) acrylate and / or methyl (meth) acrylate are particularly preferable.

Moreover, the compound etc. which are described below can also be mentioned.
Examples of the polyoxyalkylene chain-containing (meth) acrylate monomer include ethylene oxide-modified cresol acrylate (trade name: Aronix TO-901), ethylene oxide-modified dodecyl acrylate (trade name: Aronix TO-950), and ethylene oxide-modified tridecyl. Acrylate (trade name: Aronix TO-951), 2-ethylhexyl polyethylene glycol acrylate (trade name: Aronix TO-946), 2-ethylhexyl polyethylene glycol acrylate (trade name: Aronix TO-947), 2-ethylhexyl polyethylene glycol acrylate ( Product name: Aronix TO-948), 2-ethylhexyl polyethylene glycol acrylate (Product name: Aronix TO-) 49), manufactured by Toagosei Co., Ltd.;
Ethoxy-diethylene glycol acrylate (trade name: light acrylate EC-A), methoxy-triethylene glycol acrylate (trade name: light acrylate MTG-A), methoxy-polyethylene glycol acrylate (trade name: light acrylate 130A), phenoxy-polyethylene glycol Acrylate (trade name: light acrylate P-200A), nonylphenyl-polyoxyethylene chain adduct acrylate (trade name: light acrylate NP-4EA), nonylphenyl-polyoxyethylene chain adduct acrylate (trade name: light acrylate NP) -8EA), manufactured by Kyoeisha Chemical Co., Ltd .;

Polyethylene glycol acrylate (trade name: Blemmer AE-350), polyethylene glycol methacrylate (trade name: Blemmer PE-90), polyethylene glycol methacrylate (trade name: Blemmer PE-200), polyethylene glycol methacrylate (trade name: Blemmer PE-350) ), Methoxypolyethylene glycol monoacrylate (trade name: Blemmer AME-400), methoxypolyethylene glycol methacrylate (trade name: Blemmer PME-100), methoxypolyethylene glycol methacrylate (trade name: Blemmer PME-200), methoxypolyethylene glycol methacrylate ( Product name: Bremer PME-400), Polypropylene glycol methacrylate (Product name: Bure Mer PP-500), polypropylene glycol methacrylate (trade name: Blenmer PP-800), polyethylene glycol polypropylene glycol methacrylate (trade name: Blemmer 70PEP-370B), polyethylene glycol polytetramethylene glycol methacrylate (trade name: Blemmer 50PET-800) , Octoxy polyethylene glycol polypropylene glycol monomethacrylate (trade name: Blemmer 50POEP-800B), Octoxy polyethylene glycol polyoxypropylene glycol monomethacrylate (trade name: Blemmer 50AOEP-800B), as described above, manufactured by NOF Corporation;
Methoxydiethylene glycol methacrylate (trade name: NK ester M-20G), methoxydiethylene glycol methacrylate (trade name: NK ester M-40G), methoxydiethylene glycol methacrylate (trade name: NK ester M-90G), phenoxydiethylene glycol acrylate (trade name: NK Ester AMP-20G), Shin-Nakamura Chemical Co., Ltd., and the like.

Component D may have one type of structural unit (a-5) or may have two or more types.
It is preferable that content of the monomer unit which comprises the structural unit (a-5) in the component D is 0-40 mol% with respect to all the monomer units of the component D.
In addition, when Component D has the structural unit (a-5), the content of the monomer units constituting the structural unit (a5) in Component D is 1 to 40 mol% with respect to all the monomer units of Component D. Preferably, 5-30 mol% is more preferable, and 10-25 mol% is especially preferable.

  In addition, the method for introducing each constituent unit of component D may be a polymerization method, a polymer reaction method, or a combination of these two methods. Component D can be used alone or in combination of two or more in the resin composition.

The content of Component D in the resin composition of the present invention is preferably 10 to 99% by weight, more preferably 20 to 95% by weight, based on the total solid content of the resin composition, 25 More preferably, it is -90 weight%. When the content is within this range, the pattern formability during development is good, and a cured product having a higher refractive index can be obtained. The solid content of the resin composition represents an amount excluding volatile components such as a solvent.
In addition, in the resin composition of this invention, you may use resin other than the component B and the component D together in the range which does not prevent the effect of this invention. However, the content of the resin other than Component B and Component D is preferably less than the content of Component B and the content of Component D.

(Component E) Photoacid Generator The positive photosensitive resin composition of the present invention preferably contains (Component E) a photoacid generator.
Component E 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 D 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 -Piperonylbis (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-methylphenyl) Thenyl] 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 resin composition of the present invention preferably contains an oxime sulfonate compound having at least one oxime sulfonate residue represented by the following formula (1) as component D from the viewpoint of sensitivity. 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. Represent. 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, a carbon number of 1 to 1 10 represents an alkyl group, 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 resin composition of the present invention, (Component E) 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 D, and 0.5 to 10 parts by weight More preferably it is used.

(Component F) Thermal crosslinking agent The resin composition of the present invention preferably contains (Component F) a thermal crosslinking agent. (Component F) A hardened film can be obtained by adding a thermal crosslinking agent. Component F in the present invention is other than component D.
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, an epoxy resin having an epoxy group is particularly preferable.
Specific examples of the epoxy resin having an epoxy group include an epoxy group-containing bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, aliphatic epoxy resin, and the like. it can.
Among these, bisphenol A type epoxy resins having an epoxy group, aliphatic epoxy resins having an epoxy group, and phenol novolac type epoxy resins having an epoxy group are particularly preferable.
Component F is added in an amount of preferably 0.05 to 50 parts by weight, more preferably 0.5 to 10 parts by weight, with respect to 100 parts by weight of Component D. More preferably, it is 5 parts by weight.

<Other ingredients>
The resin composition of the present invention may contain other components other than the components A to F.
As other components, it is preferable to add (Component G) sensitizer and (Component H) development accelerator from the viewpoint of sensitivity.
Furthermore, the resin composition of the present invention preferably contains (Component I) an adhesion improver from the viewpoint of substrate adhesion, and preferably contains (Component J) a basic compound from the viewpoint of liquid storage stability. From the viewpoint of coatability, it is preferable to contain (component K) a surfactant (such as a fluorosurfactant or a silicone surfactant).
Furthermore, if necessary, the resin composition of the present invention includes (Component L) an antioxidant, (Component M) a plasticizer, (Component N) a thermal radical generator, (Component O) a thermal acid generator, ( Component P) Known additives such as acid proliferating agents, ultraviolet absorbers, thickeners, and organic or inorganic suspending agents can be added.
Hereinafter, the other component which the resin composition of this invention can contain is demonstrated.

(Component G) Sensitizer In the resin composition of the present invention, (Component G) a sensitizer can be added in order to promote its decomposition in combination with the above-mentioned (Component E) photoacid generator. .
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 preferred 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, anthracenes, 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 E) the photoacid generator, from the viewpoint of achieving both sensitivity and transparency.

(Component H) Development accelerator The resin composition of the present invention preferably contains (Component H) a development accelerator.
(Component H) As the development accelerator, any compound having a development acceleration effect can be used, but a compound having at least one structure selected from the group consisting of a carboxy group, a phenolic hydroxyl group, and an alkyleneoxy group It is preferable that the compound which has a carboxy group or a phenolic hydroxyl group is more preferable. A compound having a carboxy group or a phenolic hydroxyl group protected with an acid dissociable group is also particularly preferred.
Further, the molecular weight of the (component H) development accelerator is preferably 100 to 2,000, more preferably 150 to 1,500, and particularly preferably 150 to 1,000.

Examples of the development accelerator include those having an alkyleneoxy group such as polyethylene glycol, methyl ether of polyethylene glycol, 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 H) The development accelerator may be used alone or in combination of two or more.
The addition amount of (Component H) development accelerator in the resin composition of the present invention is preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of Component D 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 I) Adhesion Improving Agent The resin composition of the present invention preferably contains (Component I) an adhesion improving agent.
The (component I) adhesion improver that can be used in the resin composition of the present invention is an insulating material such as an inorganic substance serving as a substrate, for example, a silicon compound such as silicon, silicon oxide, or silicon nitride, a metal such as gold, copper, or aluminum. It is a compound that improves the adhesion. Specific examples include silane coupling agents and thiol compounds. The silane coupling agent as the (component I) adhesion improver used in the present invention is intended to modify 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.
The content of the (Component I) adhesion improver in the resin composition of the present invention 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 Component D. preferable.

(Component J) Basic Compound The resin composition of the present invention preferably contains (Component J) a basic compound.
(Component J) 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 compounds that can be used in the present invention may be used singly or in combination of two or more.
The content of the (Component J) basic compound in the resin composition of the present invention is preferably 0.001 to 1 part by weight with respect to 100 parts by weight of Component D, and is 0.002 to 0.001. More preferably, it is 2 parts by weight.

(Component K) Surfactant (fluorine surfactant, silicone surfactant, etc.)
The resin composition of the present invention preferably contains (Component K) a surfactant (such as a fluorine-based surfactant and 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 Chemical Co., Ltd.), Florard FC430, 431 (Sumitomo 3M Co., Ltd.), MegaFuck F171F780F, F173 F176, F189, R08 (above, manufactured by DIC Corporation), Surflon S-382, SC01, 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 K) surfactant (fluorine-based surfactant, silicone-based surfactant, etc.) in the resin composition of the present invention is 10 parts by weight or less with respect to 100 parts by weight of component D content. Preferably, it is 0.01 to 10 parts by weight, more preferably 0.01 to 1 part by weight.

(Component L) Antioxidant The resin composition of the present invention may contain (Component L) an antioxidant. (Component L) By adding an antioxidant, coloring of the cured film can be prevented, or reduction in film thickness due to decomposition can be reduced.
(Component L) As an antioxidant, a well-known antioxidant can be contained. 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 L) 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 resin composition, It is particularly 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.
Further, as additives other than antioxidants, various ultraviolet absorbers described in “New Development of Polymer Additives (Nikkan Kogyo Shimbun Co., Ltd.)”, metal deactivators and the like are used as resin compositions of the present invention. It may be added to the product.

(Component M) Plasticizer The resin composition of the present invention may contain (Component M) a plasticizer.
Examples of (Component M) 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 M) plasticizer in the resin composition of the present invention is preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of the component D, and is 1 to 10 parts by weight. It is more preferable.

(Component N) Thermal radical generator The resin composition of the present invention may contain (Component N) a thermal radical generator, and contains an ethylenically unsaturated compound such as a compound having an ethylenically unsaturated double bond. When contained, it is preferable to contain (Component N) 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 N) A thermal radical generator may be used alone or in combination of two or more.
The content of the (component N) thermal radical generator in the resin composition of the present invention is preferably 0.01 to 50 parts by weight, when the content of component D is 100 parts by weight, from the viewpoint of improving film properties. 0.1-20 weight part is more preferable, and 0.5-10 weight part is the most preferable.

(Component O) Thermal Acid Generator The resin composition of the present invention may contain (Component O) a thermal acid generator.
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 molecular weight of the thermal acid generator is preferably 230 to 1,000, and more preferably 230 to 800.
The content of the thermal acid generator in the 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 D content.

(Component P) Acid Proliferator The resin composition of the present invention can use (Component P) 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 strength of the acid is preferably 3 or less, particularly preferably 2 or less, as the acid dissociation constant, pKa.
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 an acid generated from the acid generator. Examples include compounds that generate 3 or less acids.

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

(Method for producing positive photosensitive resin composition)
The method for producing the positive photosensitive resin composition of the present invention is not particularly limited, but (Component A) inorganic particles, (Component B) a dispersant having an acid group, and (Component C) a solvent are mixed to obtain a dispersion. And a polymer having (component D) (a-1) a structural unit having a group capable of leaving by acid and / or heat and (a-2) a structural unit having a crosslinking group in the dispersion, In addition, it is preferable to include a step of adding (Component E) a photoacid generator.
Moreover, in the manufacturing method of the positive photosensitive resin composition of this invention, it is preferable to mix the component A-component C beforehand, and to make a dispersion liquid.
The mixing order of component A to component C is not particularly limited, and three types may be mixed at the same time, or any two types may be mixed first and the remaining one may be added thereto. Further, a mixture of component A and a solvent may be combined with a mixture of component B and a solvent.
Examples of the solvent used for preparing the dispersion include 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-2-propanol, in addition to the above-described (Component C) solvent. -Alcohols such as pentanol, 2-pentanol, 3-pentanol, 3-methyl-1-butanol, 2-methyl-2-butanol, neopentanol, cyclopentanol, 1-hexanol, cyclohexanol, etc. Can be mentioned.
These solvents can be used singly or in combination of two or more.
The mixing means of component A to component E and other components is not particularly limited, but is preferably mixed and dispersed by using a mixing device such as a ball mill, a rod mill, a bead mill, a paint shaker, a homogenizer, or a three roll. Can be prepared.

  Moreover, when preparing a dispersion liquid beforehand using an inorganic particle, the component B, and a solvent, content of the component B with respect to the total solid of the said dispersion liquid is 0.1 from a viewpoint of a dispersibility and dispersion stability. The range of -90 weight% is preferable, the range of 5-80 weight% is more preferable, The range of 10-75 weight% is still more preferable.

Moreover, there is no restriction | limiting in particular also about addition of the component D and the component E, for example, the component D and the component E may be added to the said dispersion liquid simultaneously or sequentially as it is, and the component D and the component E are each mixed with a solvent. It may be added to the dispersion.
Moreover, there is no restriction | limiting in particular about the mixing timing of components other than the component A-component E, even if it mixes in the stage of the said dispersion liquid, you may mix after preparing the said dispersion liquid, It is preferable to mix after preparation.

(Method for producing cured product)
Although the manufacturing method of the hardened | cured material of this invention will not have a restriction | limiting in particular if it is a manufacturing method of the hardened | cured material using the positive photosensitive resin composition of this invention, At least process (a)-(c) is included in this order. A method is preferred. In addition, the shape of the cured product obtained by the method for producing a cured product of the present invention is not particularly limited, and may be arbitrary even if it is a film-shaped cured product as in the method including the following steps (a) to (c). Even if it is the shape of this, a pattern-shaped hardened | cured material may be sufficient so that it may mention later.
(A) Application step of applying the positive photosensitive resin composition of the present invention onto a substrate (b) Solvent removal step of removing the solvent from the applied resin composition (c) A resin composition from which the solvent has been removed Heat treatment step for heat treatment Each step will be described below in order.

<Coating process (process (a))>
It is preferable that the manufacturing method of the hardened | cured material of this invention includes the application | coating process which apply | coats the positive photosensitive resin composition of this invention on a board | substrate (a).
In step (a), the positive photosensitive resin composition of the present invention is applied to a predetermined substrate, and the solvent is removed by decompression and / or heating (prebaking) to form a desired dry coating film. It is preferable.
Substrate materials that can be used in the present invention include silicon, silicon dioxide, silicon nitride, alumina, glass, glass-ceramics, gallium arsenide, indium phosphide, copper, aluminum, nickel, iron, steel, copper-silicon. Examples include, but are not limited to, alloys, indium-tin oxide coated glass; organic films such as polyimide and polyester; any substrate containing patterned regions of metals, semiconductors and insulating materials. Optionally, a baking step can be performed on the substrate to remove absorbed moisture before applying the 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.

<Solvent removal step (step (b))>
It is preferable that the manufacturing method of the hardened | cured material of this invention includes the solvent removal process which removes a solvent from the apply | coated resin composition (b).
In the step (b), it is preferable that the solvent is removed from the applied film by vacuum (vacuum) and / or heating to form a dry coating film on the substrate. 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.

<Heat treatment step (step (c))>
It is preferable that the manufacturing method of the hardened | cured material of this invention includes the heat processing process (baking process) which heat-processes the resin composition from which the solvent was removed. A cured film can be formed by heat treatment.
The heat treatment temperature (baking temperature) is preferably 180 to 250 ° C., and the heat treatment time is preferably 30 to 150 minutes.
For example, as component D, (a-1-1) a monomer unit having a residue in which a carboxy group or a phenolic hydroxyl group is protected with an acid-decomposable group, and (a-2-1) an epoxy group and / or an oxetanyl group When a polymer having a monomer unit is used, in the heat treatment step, an acid-decomposable group in the monomer unit (a-1-1) is thermally decomposed to generate a carboxy group or a phenolic hydroxyl group, and an epoxy group and A cured film can be formed by crosslinking with an oxetanyl group.
When (Component F) a thermal crosslinking agent is used, it is preferable that (Component F) a thermal crosslinking agent is also thermally crosslinked in the heat treatment step.

(Resin pattern manufacturing method)
The resin pattern manufacturing method of the present invention is not particularly limited as long as it is a resin pattern manufacturing method using the positive photosensitive resin composition of the present invention, but is a method including at least steps (1) to (5) in this order. Preferably there is.
(1) Application step of applying the positive photosensitive resin composition of the present invention onto a substrate (2) Solvent removal step of removing the solvent from the applied resin composition (3) A resin composition from which the solvent has been removed (4) Development process for developing the exposed resin composition with an aqueous developer (5) Heat treatment process for heat-treating the developed resin composition Each process will be described in order below. .

<Application process (process (1))>
The resin pattern manufacturing method of the present invention preferably includes (1) a coating step of coating the positive photosensitive resin composition of the present invention on a substrate.
Step (1) is the same as step (a), and the preferred embodiment is also the same.

<Solvent removal step (step (2))>
The resin pattern manufacturing method of the present invention preferably includes (2) a solvent removal step of removing the solvent from the applied resin composition.
Step (2) is the same as step (b), and the preferred embodiment is also the same.

<Exposure process (process (3))>
The method for producing a resin pattern of the present invention preferably includes (3) an exposure step of exposing the 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.
As the actinic ray, 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.

In the case of using a laser, various lasers can be used without particular limitation by appropriately selecting the wavelength. For example, a solid (YAG) laser uses 343 nm and 355 nm, an excimer laser uses 351 nm (XeF), and a semiconductor laser uses 375 nm and 405 nm. 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.
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.
The exposure apparatus that can be used in the present invention is not particularly limited, but commercially available exposure apparatuses include Callisto (buoy technology), AEGIS (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.

  Moreover, 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 preferably includes (4) a developing step of developing the exposed resin composition with an aqueous developer.
In step (4), development is performed using an aqueous developer.
As the aqueous developer, an alkaline developer is preferable. 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; alkali metal carbonates such as sodium carbonate and potassium carbonate; sodium bicarbonate, Alkali metal bicarbonates such as potassium bicarbonate; ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline hydroxide; and aqueous solutions such as sodium silicate and sodium metasilicate 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 may include the re-exposure process which re-exposes the board | substrate in which the pattern was formed with active light between the process (4) and the process (5), but does not include it. It is preferable.
The exposure in the re-exposure process may be performed by the same means as in the exposure process. However, in the re-exposure process, it is preferable to expose the entire surface of the substrate on which the resin composition film is formed.
A preferable exposure amount in the re-exposure step is 100 to 1,000 mJ / cm ² .

<Heat treatment step (step (5))>
The method for producing a resin pattern of the present invention preferably includes a heat treatment step (baking step) for heat-treating the developed resin composition. A cured film can be formed by heat treatment.
The step (5) is the same as the step (c) except that the developed resin composition that has undergone the step (4) is used instead of the resin composition from which the solvent has been removed. The aspect is also the same.

(Transfer material)
The positive photosensitive resin composition of the present invention can be suitably used as a transfer material. Specifically, for example, the resin composition provided on the temporary support can be suitably used as a transfer material that is used by being transferred onto a substrate of a display device or a semiconductor substrate.
When a resin pattern is formed using the positive photosensitive resin composition of the present invention as a transfer material, the resin pattern manufacturing method of the present invention includes the following steps (1 ′) to (6 ′) in this order. It is preferable.
(1 ′) Application step of applying the positive photosensitive resin composition of the present invention onto a temporary support (2 ′) Solvent removal step of removing the solvent from the applied resin composition (3 ′) The solvent is removed (4 ′) An exposure step of exposing the transferred resin composition in a pattern with actinic rays (5 ′) An aqueous developer for exposing the exposed resin composition to a substrate (permanent support) (6 ') The heat treatment process which heat-processes the developed resin composition

<Coating process (process (1 '))>
The method for producing a resin pattern of the present invention preferably includes (1 ′) a coating step of coating the positive photosensitive resin composition of the present invention on a substrate.
The step (1 ′) is the same as the step (a) except that the temporary support shown below is used instead of the substrate, and the preferred embodiment is also the same.
As the temporary support, known materials such as polyester and polystyrene can be used. Among these, biaxially stretched polyethylene terephthalate is preferable from the viewpoints of cost, heat resistance, and dimensional stability.
The thickness of the temporary support is preferably 15 to 200 μm, and more preferably 30 to 150 μm.

<Solvent removal process (process (2 '))>
The method for producing a resin pattern of the present invention preferably includes (2 ′) a solvent removal step of removing the solvent from the applied resin composition.
Step (2 ′) is the same as step (b), and the preferred embodiment is also the same.

<Transfer process (process (3 '))>
The resin pattern manufacturing method of the present invention preferably includes (3 ′) a step of transferring the resin composition from which the solvent has been removed to a substrate (permanent support).
The transfer step preferably includes a step of bonding the resin composition from which the solvent has been removed to a substrate (permanent support) and a step of removing the temporary support from the resin composition attached to the substrate.
The bonding of the resin composition from which the solvent has been removed and the substrate can be performed, for example, by pressing or thermocompression bonding with a heated and / or pressurized roller or flat plate.
Specific examples include laminators and laminating methods described in JP-A-7-110575, JP-A-11-77942, JP-A-2000-334836, and JP-A-2002-148794. From this point of view, it is preferable to use the method described in JP-A-7-110575.
The method for removing the temporary support is not particularly limited. For example, the temporary support is removed by bringing an adhesive roller having an adhesive layer or the like into contact with the temporary support and peeling the temporary support from the resin composition attached to the substrate. be able to. Specifically, the temporary support may be peeled by continuously peeling the temporary support in a continuous winding manner or by gripping the end of the temporary support protruding from the substrate separated into a single wafer type. it can.
Preferable examples of the temporary support peeling method include the method described in JP-A-2006-297879 for continuous peeling and the method described in JP-A-2007-320678 for single wafer peeling.

<Exposure process (process (4 '))>
The resin pattern production method of the present invention preferably includes (4 ′) an exposure step of exposing the transferred resin composition in a pattern with actinic rays.
The step (4 ′) is the same as the step (3) except that the resin composition transferred through the step (3 ′) is used instead of the resin composition from which the solvent is removed. The preferred embodiment is also the same.

<Development process (process (5 '))>
The resin pattern production method of the present invention preferably includes (5 ′) a developing step of developing the exposed resin composition with an aqueous developer.
Step (5 ′) is the same as step (4), and the preferred embodiment is also the same.

<Heat treatment process (process (6 '))>
The method for producing a resin pattern of the present invention preferably includes (6 ′) a heat treatment step of heat-treating the developed resin composition. A cured film can be formed by heat treatment.
Step (6 ′) is the same as step (5), and the preferred embodiment is also the same.
JP, 2010-72589, A, etc. can also be referred to as a resin pattern manufacturing method in the case of forming a resin pattern using the resin composition of the present invention as a transfer material.

(Cured product, optical member)
The cured product of the present invention is not particularly limited as long as it is obtained by curing the positive photosensitive resin composition of the present invention. However, the cured product of the present invention was produced by the production method of the cured product or the resin pattern production method of the present invention. A cured product is preferred.
The cured product of the present invention can be suitably used as an optical member such as a microlens, an optical waveguide, or an antireflection film. Moreover, the hardened | cured material of this invention can be used conveniently also as a member for visibility reduction of the wiring electrode used for a touch panel. Among these, it can be particularly suitably used as a microlens.

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

<Method for measuring acid value>
The acid value of the polymer was measured by titration using potassium hydroxide.

<Preparation of dispersion D1>
A dispersion having the following composition was prepared, mixed with 17,000 parts by weight of zirconia beads (0.3 mmφ), and dispersed for 12 hours using a paint shaker. Zirconia beads (0.3 mmφ) were filtered off to obtain dispersion D1.
-Titanium dioxide (manufactured by Ishihara Sangyo Co., Ltd., trade name: TTO-51 (C), average primary particle size: 10-30 nm) 1,875 parts-Compound 1 (the following compound, Mw = 30,000, acid value: 180 mg KOH / g, 30% PGMEA solution) 2,200 parts / solvent PGMEA (propylene glycol monomethyl ether acetate)
3,425 parts

<Preparation of dispersions D2 to D11>
Dispersions D2 to D11 were obtained in the same manner as in the preparation of Dispersion D1, except that TTO-51 (C) and Compound 1 were changed to those described in Table 1, respectively.

In addition, the symbol used for the dispersion liquid of Table 1 is as showing below. In addition, the copolymerization ratio as described in the lower right of the brackets [] of the compounds 1 to 5 is a weight% ratio. Moreover, the number described in the lower right of the parenthesis () represents the number of repetitions.
TTO-55 (C): Titanium dioxide, manufactured by Ishihara Sangyo Co., Ltd., average primary particle size: 30-50 nm
RC-100: Zirconium dioxide, manufactured by Daiichi Elemental Chemical Co., Ltd., D ₅₀ : 1.5 to 4 μm
Compound 2: The following compound, Mw = 30,000, acid value: 140 mgKOH / g, 30% PGMEA solution Compound 3: The following compound, Mw = 30,000, acid value: 100 mgKOH / g, 30% PGMEA solution Compound 4: Compound, Mw = 30,000, acid value: 105 mg KOH / g, 30% PGMEA solution Compound 5: the following compound, Mw = 30,000, acid value: 60 mg KOH / g, 30% PGMEA solution

<Synthesis of polymer>
In the following synthesis examples, the following abbreviations represent the following compounds, respectively.
V-601: Dimethyl-2,2′-azobis (2-methylpropionate)
PGMEA: Propylene glycol monomethyl ether acetate

<Synthesis of Polymer P1>
Tetrahydrofuran-2-yl methacrylate (0.38 molar equivalent),
Methacrylic acid (0.12 molar equivalent),
100 parts total of (3-ethyloxetane-3-yl) methyl methacrylate (0.50 molar equivalent), and
A mixed solution of propylene glycol monomethyl ether acetate (PGMEA) (120 parts) was heated to 70 ° C. under a nitrogen stream. While stirring this mixed solution, radical polymerization initiator V-601 (dimethyl-2,2′-azobis (2-methylpropionate)), manufactured by Wako Pure Chemical Industries, Ltd., 12.0 parts) and PGMEA (80 parts) of the mixed solution was added dropwise over 3.5 hours. After the completion of dropping, the PGMEA solution of polymer P1 was obtained by reacting at 70 ° C. for 2 hours. Further, PGMEA was added to adjust the solid content concentration to 40% by weight.
The weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of the obtained polymer P1 was 15,000. The acid value was 45 mg KOH / g.

<Synthesis of Polymers P2 to P15>
Except for changing each monomer used in the synthesis of the polymer P1 to a monomer that forms each structural unit shown in Table 2, and changing the amount of the monomer that forms each structural unit to that shown in Table 2, Polymers P2 to P15 were respectively synthesized in the same manner as the synthesis of the polymer P1. The amount of radical polymerization initiator V-601 added was adjusted so that each polymer had the molecular weight shown in Table 2.

In addition, the quantity described in Table 2 is a molar ratio, and represents the copolymerization ratio of structural units derived from each monomer described in the type column. In Table 2, “-” indicates that the structural unit is not included.
Abbreviations in Table 2 are as follows.
MAEVE: 1-ethoxyethyl methacrylate MATHF: tetrahydrofuran-2-yl methacrylate OXE-30: methacrylic acid (3-ethyloxetane-3-yl) methyl (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
BzMA: benzyl methacrylate HEMA: 2-hydroxyethyl methacrylate MAA: methacrylic acid MMA: methyl methacrylate GMA: glycidyl methacrylate St: styrene

Example 1
<Preparation of positive photosensitive resin composition>
After mixing and mixing with the following composition to obtain a uniform solution, the mixture was filtered using a polyethylene filter having a pore size of 0.2 μm to prepare a positive photosensitive resin composition of Example 1.
140 parts propylene glycol monomethyl ether acetate 0.5% PGMEA solution of 1,5-diazabicyclo [4.3.0] -5-nonene
18 parts 0.2% PGMEA solution of triphenylimidazole 5 parts Polymer P1 225 parts α- (p-toluenesulfonyloxyimino) phenylacetonitrile 3 parts JER157S65 (Mitsubishi Chemical Corporation, epoxy equivalent: 200) ~ 220g / eq)
3 parts, 3-glycidoxypropyltrimethoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) 3 parts, 2.0 parts of a 2.0% PGMEA solution of the following compound W-3, 600 parts of dispersion D1

<Evaluation of remaining film ratio of unexposed area>
The obtained photosensitive resin composition was applied on a 100 mm × 100 mm glass substrate (trade name: XG, manufactured by Corning) with a spin coater so as to have a film thickness of 1.0 μm, and then on a hot plate at 90 ° C. And dried for 120 seconds (pre-baked).
Next, the film was developed with a 0.5% aqueous solution of tetramethylammonium hydroxide at 23 ° C. for 15 seconds by immersion, and further rinsed with ultrapure water for 10 seconds. Thereafter, the film thickness was further measured to determine the remaining film ratio after development with respect to 100% of the original film thickness (1.0 μm). The evaluation criteria are as shown below.
A: The residual film ratio after development is 90% or more.
○: The remaining film ratio after development is 80% or more and less than 90%.
X: The residual film rate after development is less than 80%.
Table 3 shows the evaluation results.

<Resolution evaluation>
Hexamethyldisilazane (HMDS) is used on a 100 mm × 100 mm glass substrate (trade name: XG, manufactured by Corning) treated for 3 min so that the resulting photosensitive resin composition has a thickness of 1.2 μm. The sample was coated with a spin coater and dried (prebaked) for 120 seconds on a hot plate at 90 ° C.
Next, using a ghi-line high-pressure mercury lamp exposure machine, the film was exposed through a 1% to 60% gradation mask with a line and space of 1: 1 at an illuminance of 20 mW / cm ² and 300 mJ / cm ² .
Next, the film was developed with a 0.5% aqueous solution of tetramethylammonium hydroxide at 23 ° C. for 15 seconds by immersion, and further rinsed with ultrapure water for 10 seconds. Subsequently, a pattern was obtained by heating at 220 ° C. for 45 minutes. This pattern was observed with an optical microscope.
This operation is started from the width of the mask line and space of 50 μm, and until 10 μm, the width is reduced by 5 μm by 10 μm, and the width is reduced by 1 μm. .
A: The resolution was 10 μm or less.
(Triangle | delta): The resolution exceeded 10 micrometers and was 50 micrometers or less.
X: A pattern could not be formed with a line and space width of 50 μm of the mask.

<Evaluation of transmittance>
The obtained photosensitive resin composition was applied on a 100 mm × 100 mm glass substrate (trade name: XG, manufactured by Corning) with a spin coater so as to have a film thickness of 1.0 μm, and then on a hot plate at 90 ° C. And dried for 120 seconds (pre-baked). Furthermore, the coating film was subjected to a heat treatment (post-bake) for 45 minutes in an oven at 220 ° C., and the spectrum after the post-bake was measured with MCPD-3000 manufactured by Otsuka Electronics Co., Ltd. It was evaluated by.
The transmittance at 1: 400 nm was 90% or more.
2: The transmittance at 400 nm was 85% or more and less than 90%.
3: The transmittance at 400 nm was less than 85%.

<Evaluation of ITO visibility>
An ITO pattern is formed in advance on a 100 mm × 100 mm glass substrate (trade name: XG, manufactured by Corning), and the resulting photosensitive resin composition is applied to a spin coater so as to have a film thickness of 1.0 μm. And then dried (prebaked) on a hot plate at 90 ° C. for 120 seconds.
Next, the entire surface of the substrate was exposed at an illuminance of 20 mW / cm ² and 300 mJ / cm ² using a ghi line high-pressure mercury lamp exposure machine.
Subsequently, it was heated at 220 ° C. for 45 minutes to provide a dry film of the photosensitive resin composition on the ITO pattern. The obtained board | substrate was observed with the optical microscope, and visibility evaluation was performed compared with the time when the photosensitive resin composition was not provided on the ITO pattern. The evaluation standard is so good that the ITO pattern is difficult to see.
1: The ITO pattern is almost invisible.
2: The ITO pattern appears faint.
3: The ITO pattern is clearly visible.

<Evaluation of refractive index>
The obtained photosensitive resin composition was applied onto a silicon wafer substrate using a spinner, and dried at 80 ° C. for 120 seconds to form a film having a thickness of 0.5 μm. This substrate was exposed at 300 mJ / cm ² (measured by i-line) using an ultrahigh pressure mercury lamp, and then heated in an oven at 220 ° C. for 60 minutes.
The refractive index of the cured film at 589 nm was measured using an ellipsometer VUV-VASE (manufactured by JA Woollam Japan Co., Ltd.). A higher refractive index is preferable, and 1.70 or more is more preferable.

(Examples 2-32 and Comparative Examples 1-17)
In Examples 2-32 and Comparative Examples 1-17, the positive photosensitive resin composition was the same as in Example 1 except that the dispersion and component D (polymer) were changed to those shown in Table 3, respectively. Were prepared and each evaluation was performed.

Claims (10)

(Component A) inorganic particles,
(Component B) Dispersant having an acid group,
(Component C) solvent,
(Component D) (a-1) a polymer having a structural unit having a group capable of leaving by acid and / or heat and (a-2) a structural unit having a crosslinkable group, and
(Component E) contains a photoacid generator,
A positive photosensitive resin composition, wherein the acid value of component D is 50 mgKOH / g or less.   The positive photosensitive resin composition according to claim 1, wherein Component A is metal oxide particles.   The positive photosensitive resin composition of Claim 2 whose component A is a titanium oxide particle.   The positive photosensitive resin composition according to any one of claims 1 to 3, wherein Component B is a graft copolymer having a carboxylic acid group and has an acid value of 100 mgKOH / g or more and 190 mgKOH / g or less. object.   The positive photosensitive resin composition according to claim 1, further comprising (Component F) a thermal crosslinking agent.   The positive photosensitive resin composition of any one of Claims 1-5 which is a resin composition for optical members. The manufacturing method of the hardened | cured material characterized by including at least process (a)-(c) in this order.
(A) Application process of applying the positive photosensitive resin composition according to any one of claims 1 to 6 on a substrate (b) Solvent removal process of removing a solvent from the applied resin composition (c) ) Heat treatment process for heat-treating the resin composition from which the solvent has been removed The resin pattern manufacturing method characterized by including at least process (1)-(5) in this order.
(1) Application step of applying the positive photosensitive resin composition according to any one of claims 1 to 6 on a substrate (2) Solvent removal step of removing the solvent from the applied resin composition (3) ) Exposure step of exposing the resin composition from which the solvent has been removed to a pattern with actinic rays (4) Development step of developing the exposed resin composition with an aqueous developer (5) Heat-treating the developed resin composition Heat treatment process   The hardened | cured material obtained by the manufacturing method of the hardened | cured material of Claim 7, or the resin pattern manufacturing method of Claim 8.   The optical member obtained by the manufacturing method of the hardened | cured material of Claim 7, or the resin pattern manufacturing method of Claim 8.