KR20140090177A - Positive photosensitive resin composition, method for producing cured product, method for producing resin pattern, cured product and optical member - Google Patents

Abstract

Provided is a positive photosensitive resin composition capable of obtaining a cured product that is free from opacity and cracks (cracks) and is clear. It is also an object of the present invention to provide an optical member obtained by curing the above positive photosensitive resin composition and free of cloudiness and cracks (cracks) and being clear.
The positive photosensitive resin composition of the present invention comprises (A) an inorganic particle, (B) a graft copolymer having a constitutional unit represented by any one of formulas (1) to (4), (component C) D) a polymer having (a1) a structural unit having a group which is eliminated by acid and / or heat, (a2) a structural unit having a crosslinking group, and (E) a photoacid generator.

Description

TECHNICAL FIELD [0001] The present invention relates to a positive photosensitive resin composition, a method of producing a cured product, a method of producing a resin pattern, a cured product and an optical member,

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.

BACKGROUND ART Due to the development of solid-state image pickup devices and liquid crystal display devices, it has been widely practiced to manufacture optical members such as microlenses, optical waveguides, and antireflection films by organic materials (resins).

In order to obtain a high refractive index of these optical members, it has been studied to add particles such as titanium oxide (see Patent Document 1 below).

As a conventional negative photosensitive resin composition, photosensitive resin compositions described in Patent Documents 2 to 4 are known.

Japanese Patent Application Laid-Open No. 2006-98985 Japanese Patent Application Laid-Open No. 2011-127096 Japanese Patent Application Laid-Open No. 2009-179678 Japanese Patent Application Laid-Open No. 2008-185683

An object of the present invention is to provide a positive photosensitive resin composition which can obtain a cured product free from opacity and cracks (cracks) and clear.

Another object of the present invention is to provide an optical member obtained by curing the positive photosensitive resin composition and free of whitishness and cracks (cracks) and being clear.

The above problem of the present invention is solved by the means described in the following <1> or <9> - <12>. Are described below together with <2> to <8> which are the preferred embodiments.

(Component B) a graft copolymer having a constitutional unit represented by any one of formulas (1) to (4), (component C) a solvent, (component D) (A2) a polymer having a structural unit having a crosslinking group, and (E) a photoacid generator. The positive photosensitive resin composition according to claim 1,

In the formula (1) to equation ^{(4), X 1, X} 2, X 3, X 4 and X ⁵ each independently represents a hydrogen atom or a monovalent ^{organic, W 1, W 2, W} 3 and W ⁴ each independently represent 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, n, m, p and q are each independently of 3-500 And j and k are each independently an integer of 2 to 8,

<2> The positive photosensitive resin composition according to <1>, wherein the component A is a metal oxide particle,

<3> The positive photosensitive resin composition according to <2>, wherein the component A is titanium oxide particles or zirconium oxide particles,

<4> The positive photosensitive resin composition according to any one of <1> to <3>, wherein the component B further has a structural unit having a carboxylic acid group,

<5> (Component F) The positive-working photosensitive resin composition according to any one of <1> to <4>, further comprising a heat-

<6> The positive photosensitive resin composition according to any one of <1> to <5>, wherein the acid value of the component D exceeds 50 mgKOH / g,

<7> The positive photosensitive resin composition according to any one of <1> to <6>, wherein the component B has a weight average molecular weight of less than 25,000,

&Lt; 8 > The positive photosensitive resin composition according to any one of < 1 > to < 7 &

<9> A process for producing a cured product comprising at least steps (a) to (c)

(a) a coating step of applying the positive-working photosensitive resin composition described in any one of < 1 > to < 8 &

(b) a solvent removing step of removing the solvent from the applied resin composition

(c) a heat treatment step of heat-treating the resin composition from which the solvent has been removed

&Lt; 10 > A resin pattern production method comprising at least the steps (1) to (5)

(1) a coating step of applying the positive-working photosensitive resin composition described in any one of < 1 > to < 8 &

(2) a solvent removing step of removing the solvent from the applied resin composition

(3) an exposure step of exposing the resin composition from which the solvent has been removed to a pattern shape by an actinic ray

(4) a developing step of developing the exposed resin composition with an aqueous developing solution

(5) Heat treatment process for heat-treating the developed resin composition

<11> A cured product according to <9>, a cured product obtained by the resin pattern production method described in <10>

&Lt; 12 > An optical member obtained by the process for producing a cured product described in the above item <9> or the process for producing a resin pattern described in <10>.

(Effects of the Invention)

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a positive photosensitive resin composition which can obtain a cured product free from opacity and cracks (cracks) and clear.

Further, according to the present invention, it is possible to provide an optical member obtained by curing the above positive photosensitive resin composition and free of opacity and crack (crack) and being clear.

Hereinafter, the resin composition of the present invention will be described in detail.

The term "lower limit to upper limit" in the present invention indicates "lower limit to upper limit" and "upper limit to lower limit" indicates "upper limit to lower limit". That is, a numerical range including an upper limit and a lower limit.

In the present invention, the term &quot; (component A) inorganic particle &quot;, etc. may be simply referred to as &quot; component A &quot; (a-1) &quot;.

In the present specification, the notation in which the substituent and the non-substituent are not described in the notation of the group (atomic group) includes not only a substituent but also a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (an unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

In the present invention, &quot; mass% &quot; and &quot; weight% &quot; are agreement, and &quot; mass part &quot;

(Positive photosensitive resin composition)

Each component constituting the positive photosensitive resin composition will be described below.

The positive photosensitive resin composition of the present invention (hereinafter, simply referred to as "photosensitive resin composition" or "resin composition") may be any one of (Component A) inorganic particles and (Component B) any one of formulas (1) (A) a polymer having a constituent unit having (a-1) an acid and / or a heat-removable group and (a-2) a constituent unit having a crosslinking group, , And (E) a photoacid generator.

In the formula (1) to equation ^{(4), X 1, X} 2, X 3, X 4 and X ⁵ each independently represents a hydrogen atom or a monovalent ^{organic, W 1, W 2, W} 3 and W ⁴ each independently represent 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, n, m, p and q are each independently of 3-500 And j and k are each independently an integer of 2 to 8,

In addition, the resin composition of the present invention is preferably a resin composition having properties of being cured by heat. The resin composition of the present invention is particularly preferably a thermosetting and photosensitive resin composition.

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 does not contain a 1,2-quinonediazide compound as a photoacid generator that is sensitive to an actinic ray. The 1,2-quinonediazide compound generates a carboxy group by a sequential photochemical reaction, but its quantum yield is necessarily 1 or less.

On the other hand, the (Component E) photoacid generator used in the present invention acts as a catalyst against the deprotection of an acid-protected acid generated by the action of an actinic ray, so that the acid generated by the action of one photon is protected The quantum yield is greater than 1, for example, a large value such as 10, contributing to the reaction, and a high sensitivity is obtained as a result of so-called chemical amplification.

The positive photosensitive resin composition of the present invention is a resin composition for reducing visibility of optical members such as a microlens, an optical waveguide, an antireflection film, a sealing material for LED and a chip coating material for LED, or a wiring electrode used for a touch panel And is more preferably a resin composition for a micro lens. A composition for reducing visibility of a wiring electrode used in a touch panel is a composition for a member which reduces the visibility of wiring electrodes used in a touch panel, that is, makes it difficult to see wiring electrodes. For example, ITO (indium tin oxide) And the positive photosensitive resin composition of the present invention can be suitably used for the above applications.

When the inorganic particles are added to the positive photosensitive resin composition for the purpose of controlling the refractive index or the light transmittance, the present inventors have found that even if the dispersion is uniform and clear in the state of the composition, the composition becomes cloudy at the time of coating, It is found that there is a problem that it is cracked.

As a result of a detailed examination, the inventors of the present invention have concluded that the positive photosensitive resin composition containing the components A to E is believed to be caused by the interaction of the three components of the flax component A, the component B and the component D, ), And found a clear cured product.

(Component A)

The resin composition of the present invention contains inorganic particles for the purpose of controlling the refractive index and light transmittance.

The component A preferably has a refractive index higher than that of the resin composition made of a material other than the above-mentioned particles. Specifically, particles having a refractive index of 1.50 or higher in light having a wavelength of 400 to 750 nm are more preferable, and a refractive index is 1.70 Or more, more preferably 1.90 or more.

Here, when the refractive index in the light having the wavelength of 400 to 750 nm is 1.50 or more, it means that the average refractive index in the light having the wavelength in the above range is 1.50 or more. In all the light having the wavelength in the above range It is not necessary that the refractive index is 1.50 or more. The average refractive index is a value obtained by dividing the total sum of measured values of the refractive index for each light having a wavelength in the above range by the number of measurement points.

As inorganic particles having such a high refractive index, inorganic oxide particles are preferable, and metal oxide particles are more preferable because of high transparency and light transmittance.

As inorganic oxide particles having high light transmittance and high refractive index, inorganic oxide particles such as Be, Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Gd, Tb, Dy, Yb, Lu, Ti, Zr, Hf, Oxide particles containing atoms such as Zn, B, Al, Si, Ge, Sn, Pb, Bi and Te are preferable and titanium oxide, zinc oxide, zirconium oxide, indium / tin oxide or antimony / Titanium oxide particles or zirconium oxide are more preferable, titanium oxide is particularly preferable, and titanium dioxide is most preferable. As the titanium dioxide, a rutile type having a particularly high refractive index is preferable. These inorganic particles may be treated with an organic material to impart dispersion stability.

From the viewpoint of transparency of the resin composition, the average primary particle diameter of the component A is preferably from 1 to 300 nm, particularly preferably from 3 to 80 nm. Here, the average primary particle diameter of the particles refers to the arithmetic mean of 200 particle diameters of arbitrary particles measured by an electron microscope. When the shape of the particle is not spherical, the longest side is a 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 and light transmittance required for the optical member obtained by the resin composition, By mass to 80% by mass, and more preferably from 10 to 70% by mass.

(Component B) A graft copolymer having a constitutional unit represented by any one of formulas (1) to (4)

The positive photosensitive resin composition of the present invention contains (Component B) a graft copolymer having a constitutional unit represented by any one of formulas (1) to (4).

In the formula (1) to equation ^{(4), X 1, X} 2, X 3, X 4 and X ⁵ each independently represents a hydrogen atom or a monovalent ^{organic, W 1, W 2, W} 3 and W ⁴ each independently represent 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, n, m, p and q are each independently of 3-500 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, More preferably a hydrogen atom or a methyl group, and particularly preferably a methyl group.

In the formulas (1) to (4), W ¹ , W ² , W ³ and W ⁴ each independently represents an oxygen atom or NH, particularly preferably an oxygen atom.

In the formula (3), R 'each independently represents a branched or straight chain alkylene group (preferably 1 to 10 carbon atoms, more preferably 2 or 3), and from the viewpoint of dispersion stability, -CH ₂ -CH (CH ₃ ) -, or a group represented by -CH (CH ₃ ) -CH ₂ -.

As R 'in the formula (3), one kind of component B may be used by mixing two or more kinds of R' having different structures.

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. Specifically, the following linking groups (Y-1) to (Y-21) may be mentioned. In the following structure, A means a bond with the left terminal group of Y ¹ , Y ² , Y ³ or Y ⁴ in formulas (1) to (4) Y ¹ , Y ² , Y ³ or Y ⁴ in the formula (1). Of the structures shown below, (Y-2) and (Y-13) are more preferable from the viewpoint of simplicity 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 organic group, 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 them, Z ¹ and Z ² are each independently preferably an alkyl group having 5 to ²⁴ carbon atoms, more preferably a branched alkyl group having 5 to 24 carbon atoms or a cyclic alkyl group having 5 to ²⁴ carbon atoms, from the viewpoint of improving dispersibility. Z ³ is preferably a hydroxyl group, an alkoxy group or an aryloxy group, 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 3 to 500, preferably an integer of 5 to 50, and more preferably an integer of 10 to 30.

In the formulas (1) and (2), j and k each independently represent an integer of 2 to 8, preferably an integer of 3 to 6 from the viewpoints of dispersion stability and developability, more preferably 4 or 5 , 5 is most preferable.

In formula (4), each R independently represents a hydrogen atom or a monovalent organic group, and is preferably a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group, and is preferably a hydrogen atom or an alkyl group desirable. When R is an alkyl group, the alkyl group is preferably a straight chain alkyl group having 1 to 20 carbon atoms, a branched chain alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 5 to 20 carbon atoms, more preferably a straight chain alkyl group having 1 to 20 carbon atoms And a straight chain alkyl group having 1 to 6 carbon atoms is particularly preferable.

In addition, as R in the formula (4), one kind of component B may contain two or more Rs having different structures.

The content of the constituent unit represented by any one of the formulas (1) to (4) in the component B [when the constituent unit represented by any one of the formulas (1) to (4) Is preferably in the range of 10 to 90 mass%, more preferably in the range of 10 to 70 mass%, and further preferably in the range of 10 to 30 mass% with respect to the total mass of the component B in terms of mass. Within this range, the dispersibility of the inorganic particles is excellent, and the developability of the photosensitive resin composition is improved.

The resin composition of the present invention may contain component B alone or may contain component B of two or more different structures.

The component B preferably has a structural unit represented by any one of the formulas (1) to (3) among the constituent units represented by any one of the formulas (1) to (4) (3), and more preferably a structural unit represented by the formula (1).

The component B is preferably a graft copolymer having at least a constituent unit represented by any one of formulas (1) to (4) and a constituent unit having an acid group.

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, and from the viewpoint of adsorption and dispersibility into titanium dioxide, at least one kind selected from the group consisting of carboxylic acid group, And a carboxylic acid group is particularly preferable. These acid groups can be used singly or in combination of two or more kinds.

Among them, the component B is particularly preferably a graft copolymer having at least a constitutional unit represented by any one of the formulas (1) to (4) and a constitutional unit derived from a (meth) acrylic acid or a phthalic acid monoester structure .

The acid value of the component B is preferably in the range of 5.0 mgKOH / g or more and 200 mgKOH / g or less, more preferably 10 mgKOH / g or more and 195 mgKOH / g or less, more preferably 15 mgKOH / g or more And more preferably not more than 190 mg KOH / g. When the acid value is 200 mgKOH / g or less, the pattern peeling at the time of development is inhibited. When the acid value is 5.0 mgKOH / g or more, the alkali developability is good.

The acid value of the component B in the present invention can be calculated from the average content of the acid groups in the component B, for example. Component B having a desired acid value can be obtained by changing the content of the acid group-containing structural unit constituting the component B.

The method for measuring the acid value of the component B is not particularly limited and can be measured by a known method. However, the method can be suitably measured by a method similar to the method for measuring the acid value of the component D to be described later.

The weight average molecular weight of the component B is preferably from 10,000 to 300,000, more preferably from 15,000 to 200,000, still more preferably from 15,000 to 100,000, even more preferably from 15,000 to 50,000 desirable. The weight average molecular weight of component B is preferably less than 25,000. The weight average molecular weight of the resin can be measured by GPC (Gel Permeation Chromatography), for example.

As specific examples of the component B, the following compounds 1 to 6 can be preferably exemplified. In the following formulas, x and y represent mass%, and x: y is preferably 50:50 to 95: 5, more preferably 70:30 to 90:10.

The content of the component B in the resin composition of the present invention is preferably 50 to 3,000 parts by mass, more preferably 100 to 2,000 parts by mass, and further preferably 150 to 1,500 parts by mass per 100 parts by mass of the content of the component A.

(Component C) Solvent

The resin composition of the present invention (component C) contains a solvent.

It is preferable that the resin composition of the present invention is prepared as a solution in which the component A and the component B, and any other components of the various additives described below are dissolved or dispersed in the (component C) solvent.

As the solvent (component C) used in the resin composition of the present invention, known solvents can be used, and examples thereof include 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, di Propylene glycol monoalkyl ether acetates, esters, ketones, amides, lactones, and the like.

Of these 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 solvents usable in the present invention may be used alone or in combination of two or more.

The content of the (component C) solvent in the resin composition of the present invention is preferably 50 to 3,000 parts by mass, more preferably 100 to 2,000 parts by mass, further preferably 150 to 1,500 parts by mass, per 100 parts by mass of the content of the component D Do.

(Component D) A polymer having a structural unit (a-1) having a structural unit having a group dissociated by an acid and / or heat and (a-2) a structural unit having a crosslinking group

The positive photosensitive resin composition of the present invention is a positive photosensitive resin composition comprising a constituent unit (component D) having a structural unit having (a-1) an acid and / or a thermal eliminator (also simply referred to as a " Units. &Lt; / RTI &gt;

The component D is preferably a polymer having no sulfur atom from the viewpoint of processability in the fields of solid-state imaging devices and liquid crystal display devices.

Component D preferably contains a structural unit having (a-3) an alkali-soluble group and / or a structural unit having an aromatic ring (a-4) in addition to the structural units (a-1) and Do. The component D may contain the structural unit (a-5) other than the monomer units (a-1) to (a-4).

The "constituent unit" in the present invention includes not only a monomer unit formed from one molecule of a monomer but also a constituent unit in which a monomer unit formed from one monomer molecule is modified by a polymer reaction or the like.

The weight average molecular weight (Mw) of the component D is preferably 3,000 or more, more preferably 5,000 or more, further preferably 10,000 or more, further preferably 1,000,000 or less, more preferably 80,000 or less, and even more preferably 60,000 or less . Within this range, good resolution is 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 (all manufactured by Tosoh Corporation) for the column.

Component D is preferably an acrylic polymer.

The "acrylic polymer" in the present invention is an addition polymerization type resin and is a polymer containing a monomer unit derived from (meth) acrylic acid or an ester thereof, and is a monomer other than a monomer unit derived from (meth) acrylic acid or an ester thereof Unit, for example, a monomer unit derived from a styrene or a monomer unit derived from a vinyl compound. Component D may contain both monomer units derived from (meth) acrylic acid and monomer units derived from (meth) acrylic acid esters.

In the present specification, the term "structural unit derived from (meth) acrylic acid or an ester thereof" is also referred to as "acrylic structural unit". Further, (meth) acrylic acid is collectively referred to as 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) a structural unit having a group which is eliminated by an acid and / or heat

Component D has at least a constituent unit having (a-1) an acid and / or a group which is desorbed by heat.

The group which is cleaved by the acid and / or the heat may be a group which is cleaved by an acid, a group which is cleaved by heat or a group which is cleaved by an acid and heat. However, Or a group which is eliminated by acid and heat.

The group which is cleaved at least by an acid includes, for example, a group protected with an acid-decomposable group.

From the viewpoints of sensitivity and resolution, it is preferable that the structural unit (a-1) is a structural unit (a-1-1) having a carboxyl group or a group in which the phenolic hydroxyl group is protected with an acid-decomposable group.

Component D is preferably a resin that is alkali-insoluble 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.

The term "alkali solubility" in the present invention means that the solution of the compound (resin) is coated on a substrate and the coating film (thickness: 4 μm) of the compound (resin) formed by heating at 90 ° C. for 2 minutes is 23 Means that the dissolution rate of the compound (resin) in an aqueous solution of tetramethylammonium hydroxide of 0.4% by mass or more is 0.01 m / sec or more. The term &quot; alkali insoluble &quot; means that the solution of the compound The dissolution rate of the coating film (thickness: 4 mu m) of the compound (resin) formed by heating for minute in a 0.4 mass% tetramethylammonium hydroxide aqueous solution at 23 deg. C is less than 0.01 mu m / second, preferably 0.005 mu m / Sec &lt; / RTI &gt;

[Structural unit (a-1-1) in which a carboxyl group or a phenolic hydroxyl group has a group protected with an acid-decomposable group]

Component D preferably has a carboxyl group or a structural unit (a-1-1) having a group in which the phenolic hydroxyl group is protected with an acid-decomposable group.

By having the constituent unit (a-1-1) in the component D, a highly sensitive resin composition can be obtained. The constitutional unit having a carboxyl group protected with an acid-decomposable group is characterized in that the phenolic hydroxyl group has a faster phenomenon than a constitutional unit having a group protected with an acid-decomposable group. Therefore, when a rapid development is desired, a structural unit having a carboxyl group protected with an acid-decomposable group is preferable. On the contrary, when it is desired to slow the development, it is preferable to use a structural unit having a group in which the phenolic hydroxyl group is protected with an acid-decomposable group.

As the acid decomposable group, a 1-ethoxyethyl group or a tetrahydrofuranyl group is particularly preferable, and a tetrahydrofuranyl group is most preferable.

[Structural unit (a-1-2) having carboxyl group protected group by acid-decomposable group]

- a constituent unit having a carboxyl group -

Examples of the structural unit having a carboxyl group include structural units derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule such as an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, and an unsaturated tricarboxylic acid. .

As the unsaturated carboxylic acid to be used for obtaining the constituent unit having a carboxyl group, those exemplified below are used. That is, examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid,? -Chloroacrylic acid, cinnamic acid, and the like. Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid. The unsaturated polycarboxylic acid used for obtaining a monomer unit having a carboxyl group may be an acid anhydride thereof. Specific examples thereof include maleic anhydride, itaconic anhydride, and citraconic anhydride. The unsaturated polycarboxylic acid may be a mono (2-methacryloyloxyalkyl) ester of a polycarboxylic acid, for example, mono (2-acryloyloxyethyl) succinate, mono Mono (2-acryloyloxyethyl) phthalate mono (2-methacryloyloxyethyl), and the like.

The unsaturated polycarboxylic acid may be a mono (meth) acrylate of the both terminal dicarboxylic polymers thereof, and examples thereof include ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate. have.

Examples of the unsaturated carboxylic acid include acrylic acid-2-carboxyethyl ester, methacrylic acid-2-carboxyethyl ester, maleic acid monoalkyl ester, fumaric acid monoalkyl ester and 4-carboxystyrene.

Among them, acrylic acid, methacrylic acid, or anhydride of unsaturated polycarboxylic acid is preferably used to form a structural unit having a carboxyl group from the viewpoint of developability, and acrylic acid or methacrylic acid is more preferably used.

The constituent unit having a carboxyl group may be composed of one kind alone, or may be composed of two or more kinds.

The constituent unit having a carboxyl group may be a constituent unit obtained by reacting a monomer unit having a hydroxyl group with an acid anhydride.

Specific examples of the acid anhydrides include dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and anhydrous chlorendic acid; And acid anhydrides such as trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic acid anhydride, and biphenyltetracarboxylic acid anhydride. Of these, phthalic anhydride, tetrahydrophthalic anhydride, or succinic anhydride are preferable from the viewpoint of developability.

From the viewpoint of developability, the reaction rate of the acid anhydride to the hydroxyl group is preferably from 10 to 100 mol%, more preferably from 30 to 100 mol%.

- a structural unit (a-1-2) having a group in which the carboxyl group is protected with an acid-decomposable group -

The constituent unit (a-1-2) having a carboxyl group protected with an acid-decomposable group is preferably a constituent unit in which the carboxyl group of the constituent unit having a carboxyl group has a group protected by an acid-decomposable group described in detail below.

As the acid decomposable group, those known as the acid decomposable group in the positive resist for KrF and the positive resist for ArF have heretofore been used and are not particularly limited. Conventionally, acid-decomposable groups include acetal-based functional groups such as tetrahydropyranyl groups which are relatively easily decomposed by an acid, t-butyl ester groups such as t-butyl ester group and t-butylcarbonate group, Butyl-based functional groups are known and can be used.

These acetal-based functional groups and t-butyl-based functional groups are functional groups capable of causing desorption even by heat.

Among these acid decomposable groups, a constituent unit in which a carboxyl group is protected in the form of an acetal is preferable from the viewpoints of sensitivity and resolution. Among the acid decomposable groups, it is more preferable that the carboxyl group is a group protected in the form of an acetal represented by the following formula (a1-1). When the carboxy group is a protected group in the form of an acetal represented by the following formula (a1-1), the whole group has a structure of -C (= O) -O-CR ¹ R ² (OR ³ ). The term &quot; acetal &quot; in the present invention includes not only acetal but also ketal.

[In the formula (a1-1), R ¹ and R ² each independently represent a hydrogen atom or an alkyl group. Except that R ¹ and R ² are both hydrogen atoms. R ³ represents an alkyl group. R ¹ or R ² and R ³ may be connected to form a cyclic ether. In addition, the broken line indicates the bonding position with other structures]

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 may be any of linear, branched and cyclic. Here, both of 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 the formula (a1-1), when R ¹ , R ² and R ³ represent an alkyl group, the alkyl group may be any of linear, branched or cyclic.

The straight-chain or branched-chain alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and more preferably 1 to 4 carbon atoms. Specific examples thereof include a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec- 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 isobonyl 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 R ¹ , R ² , and R ³ have a haloalkyl group as a substituent, R ¹ , R ² , and R ³ have an aralkyl group when they have an aryl group as a substituent.

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.

The aryl group is preferably an aryl group having 6 to 20 carbon atoms, and more preferably an aryl group having 6 to 12 carbon atoms. Specific examples thereof include phenyl group,? -Methylphenyl group, naphthyl group and the like.

The aralkyl group is preferably an aralkyl group having 7 to 32 carbon atoms, more preferably an aralkyl group having 7 to 20 carbon atoms. Specifically, benzyl group,? -Methylbenzyl group, phenethyl group, naphthylmethyl group and the like can be exemplified.

The alkoxy group is preferably an alkoxy group having 1 to 6 carbon atoms, more preferably an alkoxy group having 1 to 4 carbon atoms, and still more preferably a methoxy group or an ethoxy group.

When the alkyl group is a cycloalkyl group, the cycloalkyl group may have a linear or branched alkyl group having from 1 to 10 carbon atoms as a substituent. When the alkyl group is a straight chain or branched chain alkyl group, May have a cycloalkyl group.

These substituents may be further substituted by the above substituents.

In the formula (a1-1), when R ¹ , R ² and R ³ represent an aryl group, the aryl group preferably has 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms. The aryl group may have a substituent, and as the substituent, an alkyl group having 1 to 6 carbon atoms is preferably exemplified. Examples of the aryl group include a phenyl group, a tolyl group, a silyl group, a cumenyl group and a 1-naphthyl group.

Further, R ¹ , R ² and R ³ may bond 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 a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a tetrahydrofuranyl group, An adamantyl group, and a tetrahydropyranyl group. Among them, a tetrahydrofuranyl group is preferable.

In formula (a1-1), it is preferable that either R ¹ or R ² is a hydrogen atom or a methyl group.

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

R ¹¹ represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or a methyl group.

R ¹² and R ¹³ are -CH (R ¹² ) (R ¹³ ), agrees with R ² in formula (a1-1), and R ¹⁴ corresponds to R ¹ in formula (a1-1) , R &lt; ¹⁵ &gt; is the same as R &lt; ³ &gt; in the formula (a1-1), and their preferable ranges are also the same.

The above-mentioned synthesis may be carried out by previously copolymerizing (meth) acrylic acid with other monomers, and then reacting with vinyl ether in the presence of an acid catalyst.

Specific preferred examples of the structural unit (a-1-2) having a group in which the carboxyl 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) in which the phenolic hydroxyl group has a group protected with an acid-decomposable group]

- a constituent unit having a phenolic hydroxyl group -

Examples of the structural unit having a phenolic hydroxyl group include a structural unit in a hydroxystyrene-based monomer unit or a novolac-based resin. Among the constituent units having a phenolic hydroxyl group, the constituent units represented by the formula (a1-2) are preferable from the viewpoints of transparency and sensitivity.

(Wherein 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, a represents an integer of 1 to 5 , b represents an integer of 0 to 4, and a + b is 5 or less. When two or more R &lt; ²² &gt; are present, these R &lt; ²² &gt;

In formula (a1-2), R ²⁰ represents a hydrogen atom or a methyl group, and is preferably a methyl group.

In formula (a1-2), R ²¹ represents a single bond or a divalent linking group. In the case of a single crystal combination, the sensitivity can be improved and the transparency of the cured film can be further improved. Examples of the divalent linking group of R ²¹ include an alkylene group and specific examples of R ²¹ is an alkylene group include a methylene group, an ethylene group, a propylene group, an isopropylene group, an n-butylene group, an isobutylene group, Pentylene group, isopentylene group, neopentylene group, hexylene group and the like. Among them, 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.

In the formula (a1-2), a represents an integer of 1 to 5, but from the viewpoint of the effects of the present invention, and from the viewpoint of easy production, a is preferably 1 or 2, and a is 1 Is more preferable.

It is preferable that the bonding position of the hydroxyl group in the benzene ring is bonded to the 4-position when the carbon atom bonded to R ²¹ is the reference (1-position).

R ²² in the formula (a1-2) is a halogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms. Specific examples include a fluorine atom, a chlorine atom, a bromine atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert- butyl group, a pentyl group, an isopentyl group and a neopentyl group . Among them, a chlorine atom, a bromine atom, a methyl group or an ethyl group is preferable in view of easiness of production.

B represents 0 or an integer of 1 to 4;

- a structural unit having a group in which the phenolic hydroxyl group is protected with an acid-

The constituent unit in which the phenolic hydroxyl group has a group protected by an acid-decomposable group is a constituent unit in which the phenolic hydroxyl group of the constituent unit having a phenolic hydroxyl group has a group protected by an acid-decomposable group described in detail below.

As the acid decomposable group, a known acid dissociable group can be used, and there is no particular limitation. Among the acid decomposable groups, the phenolic hydroxyl group is preferably a structural unit having a group protected in the form of an acetal from the viewpoints of sensitivity and storage stability of the resin composition. Among the acid decomposable groups, from the viewpoint of sensitivity, it is more preferable that the phenolic hydroxyl group is a group protected in the form of an acetal represented by the formula (a1-1). When the phenolic hydroxyl group is a protected group in the form of an acetal represented by the formula (a1-1), the group as a whole has a structure of -Ar-O-CR ¹ R ² (OR ³ ). Ar represents an arylene group.

Preferable 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 radically polymerizable monomer used for forming the structural unit having a group in which the phenolic hydroxyl group is protected in the form of an acetal include a 1-alkoxyalkyl protected product of hydroxystyrene, a tetrahydropyranyl Alkoxyalkyl protected form of? -Methylhydroxystyrene, tetrahydrothiopyranyl protected form of? -Methyl-hydroxystyrene, 1-alkoxyalkyl protected form of 4-hydroxyphenyl methacrylate, 4- And a tetrahydropyranyl protected form of hydroxyphenyl methacrylate.

The acetal protecting group of the phenolic hydroxyl group is preferably the formula (a1-1). These may be used alone or in combination of two or more.

Specific preferred examples of the monomer unit (a-1-3) include the following constitutional units, but the present invention is not limited thereto. R in the structural unit shown below represents a hydrogen atom or a methyl group.

The structural unit (a-1) is preferably a monomer unit having a carboxyl group or a group in which the phenolic hydroxyl group is protected with a 1-ethoxyethyl group or a tetrahydrofuranyl group.

The content of the monomer unit constituting the constituent unit (a-1) in the component D is preferably from 3 to 70 mol%, more preferably from 10 to 65 mol%, based on the total monomer units of the component D from the viewpoint of sensitivity , More preferably from 20 to 60 mol%.

(a-2) a structural unit having a crosslinking group

Component D has at least a constituent unit having (a-2) a crosslinking group.

The crosslinking group is not particularly limited as long as it is a group which causes a curing reaction by a heat treatment. Preferable examples of the type of the structural unit having a crosslinking group include 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 ethylenic unsaturated group. More specifically, the following can be mentioned.

The structural unit (a-2) is preferably a structural unit (a-2-1) having an epoxy group and / or an oxetanyl group from the viewpoints of storage stability and cured film characteristics.

<Structural unit (a-2-1) having an epoxy group and / or an oxetanyl group>

The component D preferably has the structural unit (a-2-1) having an epoxy group and / or an oxetanyl group. Component D may have both of a structural unit having an epoxy group and a structural unit having an oxetanyl group. From the viewpoint of transparency of the cured product, the component D preferably has a constituent unit having an oxetanyl group.

The group having an epoxy group is not particularly limited as long as it has an epoxy ring, but a glycidyl group and a 3,4-epoxycyclohexylmethyl group can be preferably exemplified.

The group having an oxetanyl group is not particularly limited as long as it has an oxetanyl ring, but (3-ethyloxetan-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 may contain at least one epoxy group and at least one oxetanyl group, at least two epoxy groups, But not limited to, a total of 1 to 3 epoxy groups and / or oxetanyl groups, more preferably one or two epoxy groups and / or oxetanyl groups in total, More preferably an epoxy group or an oxetanyl group.

Specific examples of the radical polymerizable monomer used for forming the structural unit having an epoxy group include glycidyl acrylate, glycidyl methacrylate, glycidyl? -Ethyl acrylate, glycidyl? -N-propyl acrylate Dicumyl acrylate, glycidyl alpha-n-butyl acrylate, 3,4-epoxybutyl acrylate, methacrylic acid-3,4-epoxybutyl acrylate, Heptyl, α-ethyl acrylate-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, and Japanese Patent No. 4168443 Compounds containing an alicyclic epoxy skeleton described in &quot;

Examples of the radically polymerizable monomer used for forming the oxetanyl group-containing structural unit include (meth) acrylic esters having an oxetanyl group as described in paragraphs 0011 to 0016 of JP-A No. 2001-330953 .

Examples of the radically polymerizable monomer used for forming the structural unit (a-2-1) are a monomer containing a methacrylic acid ester structure and a monomer containing an acrylic ester structure.

Among these monomers, glycidyl methacrylate, glycidyl acrylate, compounds containing an alicyclic epoxy skeleton described in paragraphs 0034 to 0035 of Japanese Patent No. 4168443 and compounds disclosed in JP-A-2001-330953 (Meta) acrylic acid esters having an oxetanyl group as described in paragraphs 0011 to 0016 of Japanese Patent Application Laid-

Particularly preferred from the viewpoint of heat-resistant transparency are structural units derived from any one of acrylic acid (3-ethyloxetan-3-yl) methyl and methacrylic acid (3-ethyloxetan-3-yl) methyl.

These structural units (a-2-1) may be used alone or in combination of two or more.

Specific preferred examples of the structural unit (a-2-1) include the following structural units.

<Structural unit having an ethylenically unsaturated group (a-2-2)>

As the structural unit (a-2) having a crosslinking group, a structural unit (a-2-2) having an ethylenic unsaturated group can be mentioned.

The structural unit (a-2-2) having an ethylenically unsaturated group is preferably a structural unit having an ethylenic unsaturated group in its side chain, more preferably a structural unit having an ethylenic unsaturated group at its terminal and a side chain of 3 to 16 carbon atoms , And a structural unit having a side chain represented by the formula (a2-2-2) are more preferable.

(In the 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, but preferably includes an alkenyl group, a cycloalkenyl group, an arylene group, or a group obtained by combining these groups, and further includes a bond such as an ester bond, an ether bond, an amide 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 unit constituting the constituent unit (a-2) in the component D is preferably 5 to 60 mol%, more preferably 10 to 55 mol%, and still more preferably 20 to 50 mol% based on the total monomer units of the component D. Mol% is particularly preferable. By containing the structural unit (a-2) in the above ratio, physical properties of the cured film are improved.

(a-3) a structural unit having an alkali-soluble group

The component D preferably has the structural unit (a-3) having an alkali-soluble group.

The structural unit (a-3) having an alkali-soluble group has a function of imparting alkali solubility to the component D. By this, since the component D is dissolved in the alkali solution (developer) at the time of development, the component D containing the constituent unit (a-3) can be easily developed by the developer. Further, the alkali-soluble group-containing monomer may be reacted with a crosslinking agent using a crosslinking agent or with an epoxy group or an oxetane group (for example, a group derived from the structural unit (a-2-1)) present in the molecule of the component D To give hardness to the obtained cured product.

The alkali-soluble group in the structural unit (a-3) having an alkali-soluble group may be a group ordinarily used in the field of resists, and examples thereof include a carboxyl group and a phenolic hydroxyl group. Representative examples of the alkali-soluble group-containing structural unit (a-3) include, but are not limited to, an unsaturated carboxylic acid or its acid anhydride, hydroxystyrene or a derivative thereof.

As the structural unit (a-3), a structural unit having a carboxyl group or a structural unit having a phenolic hydroxyl group can be preferably used. Of these, an unsaturated carboxylic acid or its acid anhydride is particularly preferable.

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

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 preferably from 5 to 40 mol% based on the total monomer units of the component D , More preferably 10 to 25 mol%, and particularly preferably 15 to 20 mol%. Incorporation of the structural unit (a-3) at the above ratio improves developability.

It is also preferable that the acid value of the component D exceeds 50 mg KOH / g.

The acid value of the component D in the positive photosensitive resin composition of the present invention is an acid value in the presence of the structural unit (a-1) having a leaving group. For example, when the structural unit (a-1) is a structural unit having a group protected with an acid-decomposable group, it is needless to say that the acid value of the component D after the removal of the leaving group is higher than that before the removal of the acid value.

The method for measuring the acid value is not particularly limited and a known method can be used, but it is preferable to measure the acid value by the following method.

The method for measuring the acid value in the present invention is not particularly limited and can be appropriately selected from among known methods. For example, a titration method can be exemplified. A method of measuring an acid value by titration using potassium hydroxide is preferable .

(a-4) a structural unit having an aromatic ring

Component D is preferably a structural unit other than the structural units (a-1) to (a-3) and has a structural unit (a-4) having an aromatic ring from the viewpoint of the refractive index.

Examples of the monomer forming the structural unit (a-4) include styrenes, (meth) acrylic esters having an aromatic ring, and the like.

Among these, styrene-derived structural units and benzyl (meth) acrylate-derived structural units are preferably used, and benzyl methacrylate-derived structural units are more preferred.

When the component D has the structural unit (a-4), the content of the monomer unit constituting the structural unit (a-4) in the component D is preferably 5 to 35 mol% based on the total monomer units of the component D , More preferably 10 to 30 mol%, and particularly preferably 15 to 25 mol%. By containing the structural unit (a-4) in the above ratio, the physical properties of the cured film are improved.

(a-5) Other structural units

The component D may have the structural unit (a-5) other than the structural units (a-1) to (a-4) within the range not hindering the effect of the present invention.

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 2004-264623 A [ except for the monomers which form (a-1) to (a-4).

Examples of the radically polymerizable monomer used for forming the structural unit (a-5) include (meth) acrylic acid esters having an alicyclic structure such as dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclohexyl acrylate, (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, styrene, and the like.

Further, the compounds described below and the like are also exemplified.

Examples of the polyoxyalkylene chain-containing (meth) acrylate monomer include ethylene oxide modified cresol acrylate (Aronix TO-901), ethylene oxide modified dodecyl acrylate (Aronix TO-950), ethylene (Trade name: Aronix TO-947), 2-ethylhexyl polyethylene glycol acrylate (trade name: Aronix TO-946), 2-ethylhexyl polyethylene glycol acrylate ), 2-ethylhexyl polyethylene glycol acrylate (Aronix TO-948), 2-ethylhexyl polyethylene glycol acrylate (Aronix TO-949), manufactured by Soko Dojo Kosei Co.,

(Trade name: LIGHT ACRYLATE EU-A), methoxy-triethylene glycol acrylate (trade name: light acrylate MTG-A), methoxy-polyethylene glycol acrylate (Trade name: LIGHT ACRYLATE NP-4EA), nonylphenyl-polyoxyethylene (nonylphenyl-polyoxyethylene) acrylate (trade name: Chain adduct acrylate (trade name: light acrylate NP-8EA), manufactured by Kyoeisha Chemical Co., Ltd.;

(Trade name: Blemmer PE-200), polyethylene glycol methacrylate (trade name: Blemmer PE-90), polyethylene glycol methacrylate (trade name: Blemmer AE-350), 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 (trade name: Blemmer PME-400), polypropylene glycol methacrylate (trade name: Blemmer PP-500), polypropylene glycol methacrylate (Blemmer PP-800), polyethylene glycol polypropylene glycol methacrylate (Blemmer 70PEP-370B), polyethylene glycol polytetramethylene glycol methacrylate (trade name: : Blemmer 50PET-800), octoxypolyethylene glycol polypropylene glycol monomethacrylate (Blemmer 50POEP-800B), octoxypolyethylene glycol polyoxypropylene glycol monomethacrylate (trade name: Blemmer 50AOEP-800B) , Manufactured by Nippon Oil Corporation;

(Trade name: NK Ester M-90G), methoxyethyleneglycol methacrylate (trade name: NK Ester M-20G), methoxydiethylene glycol methacrylate (trade name: NK Ester M- , Phenoxyethylene glycol acrylate (trade name: NK Ester AMP-20G), and Shin-Nakamura Kagakukogyo Co., Ltd., and the like.

Among them, 2-hydroxyethyl (meth) acrylate and dicyclopentanyl (meth) acrylate are preferable. Component D may have one structural unit (a-5) alone or two or more structural units (a-5).

The content of the monomer unit constituting the constituent unit (a-5) in the component D is preferably 0 to 40 mol% based on the total monomer units of the component D.

When the component D contains the structural unit (a-5), the content of the monomer unit constituting the structural unit (a-5) in the component D is preferably from 1 to 40 mol% based on the total monomer units of the component D, , More preferably 5 to 30 mol%, and particularly preferably 5 to 25 mol%.

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

The content of the component D in the resin composition of the present invention is preferably from 10 to 99% by mass, more preferably from 20 to 97% by mass, further preferably from 25 to 95% by mass, based on the total solid content of the resin composition Do. When the content is within this range, the patterning property upon development is improved, and a cured product having a higher refractive index is obtained. In addition, the solid content amount of the resin composition means an amount excluding volatile components such as a solvent.

In the resin composition of the present invention, a resin other than the component B and the component D may be used in combination within a range not hindering the effect of the present invention. However, the content of the resin other than the component B and the component D is preferably smaller than the content of the component B and the content of the component D.

(Component E)

The positive photosensitive resin composition of the present invention preferably contains (Component E) a photoacid generator.

As the component E, a compound which generates an acid upon exposure to an actinic ray having a wavelength of 300 nm or more, preferably 300 to 450 nm, is preferable, but the chemical structure is not limited thereto. Also, for a photoacid generator that does not directly react with an actinic ray having a wavelength of 300 nm or more, a compound capable of generating an acid in response to an actinic ray having a wavelength of 300 nm or more by being used in combination with a sensitizer can be preferably used in combination with a sensitizer.

As the component E, a photoacid generator that generates an acid with a pKa of 4 or less is preferable, and a photoacid generator that generates an acid with a pKa of 3 or less is more preferable.

Examples of the photoacid generator include trichloromethyl-s-triazine, sulfonium salts and iodonium salts, quaternary ammonium salts, diazomethane compounds, imidosulfonate compounds and oxime sulfonate compounds . Among them, it is preferable to use an oxime sulfonate compound from the viewpoint of high sensitivity. These photoacid generators may be used alone or in combination of two or more.

Specific examples thereof include the following.

As trichloromethyl-s-triazine, there can be mentioned 2- (3-chlorophenyl) bis (4,6-trichloromethyl) (4-methylthiophenyl) bis (4,6-trichloromethyl) -s-triazine, 2- (4-methoxy -? - styryl) bis , 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] (4,6-trichloromethyl) -s-triazine, or 2- (4-methoxynaphthyl) bis (4,6-trichloromethyl) -Trichloromethyl) -s-triazine and the like.

As the diaryl iodonium salts, there may be mentioned diphenyl iodonium trifluoroacetate, diphenyl iodonium trifluoromethane sulfonate, 4-methoxyphenyl phenyl iodonium trifluoromethane sulfonate, 4-methoxyphenylphenyl iodonium (2'-hydroxy-1'-tetradecarboxy) phenyl iodonium trifluoromethanesulfonate, phenyl 4- (2'-hydroxy-1'- Iodonium hexafluoroantimonate, or phenyl-4- (2'-hydroxy-1'-tetradecaoxy) phenyliodonium p-toluenesulfonate.

As the triarylsulfonium salts, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyldiphenyl Sulfonium trifluoroacetate, 4-phenylthiophenyldiphenylsulfonium trifluoromethanesulfonate, or 4-phenylthiophenyldiphenylsulfonium trifluoroacetate.

Examples of the quaternary ammonium salts include tetramethylammonium butyltris (2,6-difluorophenyl) borate, tetramethylammonium hexyltris (p-chlorophenyl) borate, tetramethylammonium hexyltris (3-trifluoromethylphenyl) (P-chlorophenyl) borate, benzyldimethylphenylammonium hexyltris (3-trifluoromethylphenyl) borate, and the like can be used. .

Diazomethane derivatives such as bis (cyclohexylsulfonyl) diazomethane, bis (t-butylsulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane and the like.

As the imidosulfonate derivative, trifluoromethylsulfonyloxybicyclo [2.2.1] hept-5-ene-dicarboxyimide, succinimide trifluoromethylsulfonate, phthalimide trifluoromethylsulfonate , N-hydroxynaphthalimide methanesulfonate, N-hydroxy-5-norbornene-2,3-dicarboxyimide propanesulfonate, and the like.

The resin composition of the present invention preferably contains an oxime sulfonate compound having at least one oxime sulfonate structure represented by the following formula (1) as Component E from the viewpoint of sensitivity. In addition, the broken line indicates a bonding position with another chemical structure.

The oxime sulfonate compound having at least one oxime sulfonate structure represented by the above formula (1) is preferably a compound represented by the following formula (2).

^{R 1A -C (R 2A) =} NO-SO 2 -R 3A (2)

In 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, a 2-thienyl group, Or an alkoxy group or a cyano group. When R ^1A is a phenyl group, a biphenyl group, a naphthyl group or an anthranyl group, these groups may be substituted with a substituent selected from the group consisting of a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, .

In 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, a halogenated alkoxy group having 1 to 5 carbon atoms, W A naphthyl group which may be substituted by W, or an anthranyl, dialkylamino, morpholino or cyano group which may be substituted with W, 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 the 6-membered ring may be bonded to a benzene ring which may have 1 or 2 arbitrary substituents.

In formula (2), 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, W , A naphthyl group which may be substituted by W, or an anthranyl group which may be substituted by W. [ W represents 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 a halogenated alkoxy group having 1 to 5 carbon atoms .

The alkyl group having 1 to 6 carbon atoms represented by R ^1A may be a straight chain or branched chain alkyl group, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, , n-pentyl group, isoamyl group, n-hexyl group, or 2-ethylbutyl group.

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 methoxy group and ethoxy group.

When R ^1A represents a phenyl group, a biphenyl group, a naphthyl group or an anthranyl group, these groups may be substituted with a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom), a hydroxyl group, (For example, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group and a tert- butyl group), an alkoxy group having 1 to 4 carbon atoms , n-propoxy group, i-propoxy group, n-butoxy group) and a nitro group.

Specific examples of the alkyl group having 1 to 10 carbon atoms represented by R ^2A include a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i- an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, a n-decyl group and the like.

Specific examples of the alkoxy group having 1 to 10 carbon atoms represented by R ^2A include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, A n-decyloxy group, and the like.

Specific examples of the halogenated alkyl group having 1 to 5 carbon atoms represented by R ^2A include a trifluoromethyl group, a pentafluoroethyl group, a perfluoro-n-propyl group, a perfluoro-n-butyl group, - 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, Perfluoro-n-amyloxy group, and the like.

Specific examples of the phenyl group which may be substituted with W represented by R ^2A include an o-tolyl group, an m-tolyl group, a p-tolyl group, an o-ethylphenyl group, Propyl) phenyl group, p- (n-butyl) phenyl group, p- (i- butyl) phenyl group, (o-amyl) phenyl group, o- methoxyphenyl group, m-methoxyphenyl group, p-methoxyphenyl group, o-ethoxyphenyl group, (n-butoxy) phenyl group, p- (i-butoxy) phenyl group, p- (T-amyloxy) phenyl group, p- (i-amyloxy) phenyl group, p- (t-butoxy) phenyl group, Phenyl group, p-chlorophenyl group, p-bromophenyl group, p-fluorophenyl group, 2,4-dichlorophenyl group, 2,4-dibromophenyl group, 2,4-difluorophenyl group, Dichlorophenyl group, 2,4,6-tribromophenyl group, 2 , A 4,6-trifluorophenyl group, a pentachlorophenyl group, a pentabromophenyl group, a pentafluorophenyl group, and a p-biphenyl group.

Specific examples of the naphthyl group which may be substituted with W represented by R ^2A include a 2-methyl-1-naphthyl group, a 3-methyl-1-naphthyl group, a 4-methyl- Methyl-1-naphthyl group, 1-methyl-2-naphthyl group, 3-methyl-2-naphthyl group, 4-methyl Methyl-2-naphthyl group, 6-methyl-2-naphthyl group, 7-methyl-2-naphthyl group and 8-methyl-2-naphthyl group.

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

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

Specific examples of the alkyl group having 1 to 10 carbon atoms represented by R ^3A include a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i- an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, a n-decyl group and the like.

Specific examples of the alkoxy group having 1 to 10 carbon atoms represented by R ^3A include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, A n-decyloxy group, and the like.

Specific examples of the halogenated alkyl group having 1 to 5 carbon atoms represented by R ^3A include a trifluoromethyl group, a pentafluoroethyl group, a perfluoro-n-propyl group, a perfluoro-n-butyl group, a perfluoro-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, Perfluoro-n-amyloxy group, and the like.

Specific examples of the phenyl group which may be substituted with W represented by R ^3A include o-tolyl, m-tolyl, p-tolyl, o-ethylphenyl, m- Propyl) phenyl group, p- (n-butyl) phenyl group, p- (i- butyl) phenyl group, (o-amyl) phenyl group, o- methoxyphenyl group, m-methoxyphenyl group, p-methoxyphenyl group, o-ethoxyphenyl group, (n-butoxy) phenyl group, p- (i-butoxy) phenyl group, p- (T-amyloxy) phenyl group, p- (i-amyloxy) phenyl group, p- (t-butoxy) phenyl group, Phenyl group, p-chlorophenyl group, p-bromophenyl group, p-fluorophenyl group, 2,4-dichlorophenyl group, 2,4-dibromophenyl group, 2,4-difluorophenyl group, Dichlorophenyl group, 2,4,6-tribromophenyl group, 2 , A 4,6-trifluorophenyl group, a pentachlorophenyl group, a pentabromophenyl group, a pentafluorophenyl group, and a p-biphenyl group.

Specific examples of the naphthyl group which may be substituted with W represented by R ^3A include a 2-methyl-1-naphthyl group, a 3-methyl-1-naphthyl group, a 4-methyl- Methyl-1-naphthyl group, 1-methyl-2-naphthyl group, 3-methyl-2-naphthyl group, 4-methyl Methyl-2-naphthyl group, 6-methyl-2-naphthyl group, 7-methyl-2-naphthyl group and 8-methyl-2-naphthyl group.

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

The number of carbon atoms represented by W alkyl groups of 1 to 10, specific examples of the halogenated alkyl halogenated alkoxy, and the number of 1 to 5 carbon atoms in the alkoxy group, the number of 1 to 5 carbon atoms of 1 to 10 carbon atoms, examples, R ^2A or Specific examples of the alkyl group having 1 to 10 carbon atoms, the alkoxy group having 1 to 10 carbon atoms, the halogenated alkyl group having 1 to 5 carbon atoms, and the halogenated alkoxy group having 1 to 5 carbon atoms, represented by R ^3A , The same thing can be said.

R ^2A and R ^1A may combine with 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 group. Examples of the 5- or 6-membered ring include cyclopentane, cyclohexane, Pyrrole, furan, thiophene, imidazole, oxazole, thiazole, pyran, pyridine, pyrazine, morpholine, piperidine or piperazin ring. The 5-membered or 6-membered ring may be bonded to a benzene ring which may have an arbitrary substituent. Examples thereof include tetrahydronaphthalene, dihydroanthracene, indene, chroman, fluorene, xanthene or thioxanthene ring system . The 5-membered or 6-membered ring may contain a carbonyl group, and examples thereof include cyclohexadiene, naphthalene and anthrone ring systems.

One of the preferable forms of the compound represented by the formula (2) is a compound represented by the 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.

Equation (2-1) of, R ^3A, and R ^3A is a synonym of the expression (2), X is an alkyl group, an alkoxy group or a halogen atom, t represents an integer of 0~3, t is 2 Or 3, the plural Xs may be the same or different)

As the alkyl group represented by X, a linear or branched alkyl group having 1 to 4 carbon atoms is preferable. As the alkoxy group represented by X, a straight chain or branched chain alkoxy group having 1 to 4 carbon atoms is preferable. The halogen atom represented by X is preferably a chlorine atom or a fluorine atom.

t is preferably 0 or 1. In the formula (2-1), t is 1, X is a methyl group, X is a substituted position in the ortho position, R ^3A is a linear alkyl group having 1 to 10 carbon atoms, 7,7-dimethyl- A n-methyl 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 compounds (i), (ii), (iii) and (iv) Two or more types may be used in combination. The compounds (i) to (iv) are commercially available.

It may also be used in combination with other types of photoacid generators.

As a preferred form 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, a phenyl group , 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, 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. 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, a phenyl group , 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, 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.

Examples of R ^3A in the formula (2-2) include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-octyl group, a trifluoromethyl group, a pentafluoroethyl group, a perfluoro- N-butyl group, p-tolyl group, 4-chlorophenyl group or pentafluorophenyl group is preferable, and a methyl group, ethyl group, n-propyl group, n-butyl group or p-tolyl group is particularly preferable.

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.

As the alkoxy group having 1 to 4 carbon atoms represented by R ^4A , a methoxy group or an ethoxy group is preferable.

L is preferably 0 to 2, and particularly preferably 0 to 1.

In the formula (2) of the compound represented by the following, examples of preferred forms of the compounds included in the compound represented by the formula (2-2), formula (2), R ^1A is a phenyl group or a 4-methoxyphenyl group, R ^2A is 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 preferably a compound represented by the following formula (1-2).

Wherein R ¹ represents an alkyl group, an aryl group or a heteroaryl group, each R ² independently represents a hydrogen atom, an alkyl group, an aryl group or a halogen atom, R ⁶ 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,

In the resin composition of the present invention, the (Component E) photoacid generator is preferably used in an amount of 0.1 to 10 parts by mass, more preferably 0.5 to 10 parts by mass, per 100 parts by mass of the component D content.

(Component F) Heat crosslinking agent

The resin composition of the present invention (component F) preferably contains a heat crosslinking agent. (Component F) A strong cured film can be obtained by adding a heat crosslinking agent. Component F in the present invention is other than component D.

As the thermal crosslinking agent, a block isocyanate crosslinking agent, an alkoxymethyl group-containing crosslinking agent, a (meth) acrylic resin having an epoxy group or a carboxyl group having an epoxy group, and the like can be preferably exemplified. Among them, an epoxy resin having an epoxy group is particularly preferable.

Specific examples of the epoxy resin having an epoxy group include bisphenol A type epoxy resin having an epoxy group, bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, aliphatic epoxy resin and the like.

Of these, a bisphenol A type epoxy resin having an epoxy group, an aliphatic epoxy resin having an epoxy group, and a phenol novolak type epoxy resin having an epoxy group are particularly preferable.

The addition amount of the component F is preferably 0.05 to 50 parts by mass, more preferably 0.5 to 10 parts by mass, and still more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the content of the component D. [

&Lt; Other components >

The resin composition of the present invention may contain other components other than the components A to F described above.

As the other components, it is preferable to add a sensitizer (component G) and a development accelerator (component H) from the viewpoint of sensitivity.

From the viewpoint of substrate adhesion, the resin composition of the present invention preferably contains (Component I) an adhesion improver, and preferably contains a basic compound (Component J) from the viewpoint of liquid storage stability. (K) a surfactant (a fluorine-based surfactant, a silicone-based surfactant, etc.).

If necessary, the resin composition of the present invention may contain (Component L) antioxidant, (Component M) plasticizer, (Component N) thermal radical generator, (Component O) thermal acid generator, (Component P) Ultraviolet absorbers, thickeners, and organic or inorganic precipitation inhibitors.

Hereinafter, other components that the resin composition of the present invention can include will be described.

(Component G) sensitizer

In the resin composition of the present invention, a sensitizer (component G) may be added to accelerate the decomposition in combination with the aforementioned (component E) photoacid generator.

The sensitizer absorbs the actinic ray or radiation and becomes excited. The sensitizer in the excited state comes into contact with the photoacid generator to generate electron movement, energy transfer, and heat generation. As a result, the photoacid generator is decomposed by chemical change to generate an acid.

Examples of the preferable sensitizer include compounds having an absorption wavelength in the range of 350 nm to 450 nm belonging to the following compounds.

Polycyclic aromatic compounds (e.g., pyrene, perylene, triphenylene, anthracene), xanthines (for example, fluorescein, eosin, erythrosine, rhodamine B and rose bengal), xanthones , Xanthones, thioxanthones, dimethylthioxanthones, diethylthioxanthones), cyanines (for example, thiacarbocyanine, oxacarbocyanine), melocyanines (for example, Methylene blue, toluidine blue), acridines (for example, acridine orange, chloroflavin, thioxanthone, thioxanthone, Acrolein), acridine (e.g., acridone, 10-butyl-2-chloroacridone), anthraquinones (e.g., anthraquinone), squarylium Alumium), styryls, basestyryls, coumarins (for example, 7-diethylamino-4-methylcoumarin). Among these sensitizers, anthracene, acridone, coumarin and base styryl are particularly preferable.

The sensitizer may be commercially available or may be synthesized by a known synthesis method.

The addition amount of the sensitizer is preferably from 20 to 300 parts by mass, particularly preferably from 30 to 200 parts by mass, per 100 parts by mass of the (E) component of the photoacid generator from the viewpoints of 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 phenomenon of promoting development can be used, but it is preferably a compound having at least one structure selected from the group consisting of a carboxyl group, a phenolic hydroxyl group and an alkyleneoxy group, A compound having a phenolic hydroxyl group is more preferable. A compound having a carboxyl group or a phenolic hydroxyl group protected with an acid-dissociable group is also particularly preferable.

The molecular weight of the component (H) of the development accelerator is preferably 100 to 2,000, more preferably 150 to 1,500, and particularly preferably 150 to 1,000.

As examples of the development accelerator, those having an alkyleneoxy group include polyethylene glycol, methyl ether of polyethylene glycol, and compounds described in JP-A-9-222724.

Examples of compounds having a carboxyl group include compounds described in JP-A-2000-66406, JP-A-9-6001, JP-A-10-20501, JP-A-11-338150 .

Examples of compounds having a phenolic hydroxyl group include compounds disclosed in JP-A-2005-346024, JP-A-10-133366, JP-A-9-194415, JP-A-9-222724, 11-171810, JP-A-2007-121766, JP-A-9-297396, JP-A-2003-43679, etc. Among them, a phenol compound having 2 to 10 benzene ring is preferable, and a phenol compound having 2 to 5 benzene ring number is more preferable. Particularly preferred examples include phenolic compounds disclosed as dissolution accelerators in JP-A-10-133366.

(Component H) The development accelerator may be used singly or in combination of two or more.

The addition amount of the phenomenon promoter (component H) in the resin composition of the present invention is preferably from 0.1 to 30 parts by mass, more preferably from 0.2 to 20 parts by mass, more preferably from 0.2 to 20 parts by mass with respect to 100 parts by mass of the content of the component D from the viewpoints of sensitivity and residual film ratio, And most preferably 0.5 to 10 parts by mass.

(Component I) Adhesion improving agent

The resin composition of the present invention preferably contains (Component I) an adhesion improver.

The adhesion improver (component I) that can be used in the resin composition of the present invention is an adhesion promoter that improves adhesion of an inorganic substance to be a substrate, for example, a silicon compound such as silicon, silicon oxide, silicon nitride, / RTI &gt; Specific examples thereof include silane coupling agents and thiol compounds. The silane coupling agent as the (Component I) adhesion improver used in the present invention is for the purpose of modifying the interface and is not particularly limited and a known silane coupling agent can be used.

Preferable silane coupling agents include, for example,? -Aminopropyltrimethoxysilane,? -Aminopropyltriethoxysilane,? -Glycidoxypropyltrialkoxysilane,? -Glycidoxypropylalkyldialkoxysilane,? - Methacryloxypropyltrialkoxysilane,? -Mercaptopropyltrialkoxysilane,? - (3,4-epoxycyclohexyl) ethyltrialkoxysilane,? -Methacryloxypropyltrialkoxysilane,? - Silane, and vinyltrialkoxysilane.

Of these,? -Glycidoxypropyltrialkoxysilane and? -Methacryloxypropyltrialkoxysilane are more preferable, and? -Glycidoxypropyltrialkoxysilane is even more preferable.

These may be used alone or in combination of two or more.

The content of the (I) adhesion improver in the resin composition of the present invention is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, per 100 parts by mass of the content of the component D.

(Component J) Basic compound

The resin composition of the present invention preferably contains (Component J) a basic compound.

(Component J) As the basic compound, any of those used in the chemical amplification resistor can be selected and used. 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- Triethanolamine, dicyclohexylamine, dicyclohexylmethylamine, and the like.

Examples of the aromatic amine include aniline, benzylamine, N, N-dimethylaniline, and diphenylamine.

Examples of the heterocyclic amine include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl- Benzimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinic acid amide, quinoline, 8-oxy 4-methyl morpholine, 1,5-diazabicyclo [4.3.0] -5-nonene, 1, 2-diazabicyclo [4.3.0] -naphthalene, pyrazine, pyridazine, pyridine, pyrrolidine, piperidine, piperazine, morpholine, , 8-diazabicyclo [5.3.0] -7-undecene, and the like.

Examples of quaternary ammonium hydroxides 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 usable in the present invention may be used singly or in combination of two or more kinds.

The content of the (basic component) basic compound in the resin composition of the present invention is preferably 0.001 to 1 part by mass, more preferably 0.002 to 0.2 part by mass based on 100 parts by mass of the component D content.

(Component K) Surfactant (fluorine surfactant, silicone surfactant, etc.)

The resin composition of the present invention preferably contains (Component K) a surfactant (a fluorine-based surfactant, a silicon-based surfactant, etc.).

As the surfactant, a copolymer (3) containing the constituent unit A and the constituent unit B shown below may be mentioned as a preferable 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 straight chain alkylene group having 1 to 4 carbon atoms and R ²⁴ represents a hydrogen atom or a C1- P represents an integer of not less than 10% by mass and not more than 80% by mass, q represents an amount of not less than 20% by mass And n represents an integer of 1 or more and 10 or less.

L in the constituent 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 a surface to be coated, more preferably an alkyl group having 2 or 3 carbon atoms .

It is also preferable that the sum (p + q) of p and q is p + q = 100, that is, 100% by mass.

Specific examples of the fluorine-based surfactant and the silicon-based surfactant include Japanese Patent Application Laid-Open Nos. 62-36663, 61-226746, 61-226745, 62-170950, Japanese Patent Application Laid-Open Nos. 63-34540, 7-230165, 8-62834, 9-54432, 9-5988, 2001- 330953, and the like, and commercially available surfactants may also be used. Examples of commercially available surfactants that can be used include surfactants such as EFTOP EF301 and EF303 (manufactured by Mitsubishi Materials Denshi Kasei Co., Ltd.), Fluoride FC430 and 431 (manufactured by Sumitomo 3M Ltd.) F171, F780F, F173, F176, F189 and R08 (manufactured by DIC Corporation), Surflon S-382, SC01, 102, 103, 104, 105 and 106 (manufactured by Asahi Glass Co., Fluorine surfactants such as PolyFox series (manufactured by OMNOVA), and silicone surfactants. The polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicone surfactant.

These surfactants may be used singly or in combination of two or more. Further, a fluorine-based surfactant and a silicone-based surfactant may be used in combination.

The addition amount of the (K component) surfactant (fluorine surfactant, silicone surfactant, etc.) in the resin composition of the present invention is preferably 10 parts by mass or less, more preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the component D And more preferably 0.01 to 1 part by mass.

(Component L) Antioxidant

The resin composition of the present invention may contain an antioxidant (component L). (Component L) Addition of an antioxidant prevents the cured film from being colored, or it is possible to reduce the film thickness reduction due to decomposition.

(Component L) The antioxidant may contain a known antioxidant. Examples of such antioxidants include phosphorus antioxidants, hydrazides, hindered amine antioxidants, sulfur antioxidants, phenol antioxidants, ascorbic acids, zinc sulfate, sugars, nitrite salts, sulfites, thiosulfates, hydroxylamines And derivatives thereof. Of these, a phenol-based antioxidant is particularly preferable from the viewpoint of coloring of the cured film and reduction of the film thickness. These may be used singly or in combination of two or more kinds.

Examples of commercially available products of phenolic antioxidants include ADEKA STAV AO-60, ADEKA STAV AO-80 (manufactured by ADEKA Corporation), and ILKANOX 1098 (manufactured by Chiba Japan K.K.).

(Component L) The content of the antioxidant is preferably from 0.1 to 6% by mass, more preferably from 0.2 to 5% by mass, and particularly preferably from 0.5 to 4% by mass, based on the total solid content of the resin composition. With this range, sufficient transparency of the film formed can be obtained, and sensitivity at the time of pattern formation becomes good.

In addition, various ultraviolet absorbers, metal deactivators, and the like described in "New developments of polymer additive " (Nikkan Kogyo Shinbun Co., Ltd.) may be added to the resin composition of the present invention as additives other than the antioxidant.

(Component M) Plasticizer

The resin composition of the present invention may contain (Component M) a plasticizer.

(Component M) Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, didodecyl phthalate, polyethylene glycol, glycerin, dimethyl glycerine phthalate, dibutyl tartrate, dioctyl adipate, triacetyl glycerin and the like.

The content of the plasticizer (component M) in the resin composition of the present invention is preferably 0.1 to 30 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the content of the component D.

(Component N) Heat radical generator

The resin composition of the present invention may contain (component N) a thermal radical generator, and when it contains an ethylenically unsaturated compound such as a compound having an ethylenically unsaturated double bond, the component (N) . As the thermal radical generator, a known thermal radical generator may be used.

The thermal radical generator is a compound that generates radicals by the energy of heat and initiates or promotes the polymerization reaction of the polymerizable compound. By adding a thermal radical generator, the resulting cured film becomes stronger, and heat resistance and solvent resistance may be improved.

Preferred thermal radical generators include aromatic ketones, onium salt compounds, organic peroxides, thio compounds, hexaarylbimidazole compounds, ketooxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, , An azo-based compound, and a non-benzyl compound.

(Component N) One kind of thermal radical generator may be used singly or two or more kinds thereof may be used in combination.

From the viewpoint of improving the film properties, 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 mass, more preferably 0.1 to 20 parts by mass, And most preferably 0.5 to 10 parts by mass.

(Component O) Thermal acid generator

The resin composition of the present invention (component O) may contain a thermal acid generator.

The thermal acid generator is a compound generating an acid by heat, preferably a compound having a thermal decomposition point in the range of 130 ° C to 250 ° C, more preferably 150 ° C to 220 ° C, for example, Acid, a disulfonylimide, and the like.

As the generated acid, a sulfonic acid or a substituted alkylcarboxylic acid or arylcarboxylic acid having a pKa of not more than 2, and a disulfoneimide substituted with an electron-withdrawing group are preferred. 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 which does not generate an acid substantially by irradiation with exposure light and generates an acid by heat. The molecular weight of the thermal acid generator is preferably from 230 to 1,000, more preferably from 230 to 800.

The content of the thermal acid generator in the resin composition is preferably 0.5 to 20 parts by mass, more preferably 1 to 15 parts by mass, per 100 parts by mass of the component D content.

(Component P)

The resin composition of the present invention may use an acid-proliferating agent for improving the sensitivity (Component P). The acid-proliferating agent used in the present invention is a compound capable of generating an acid by further catalysing an acid catalysis to increase the concentration of an acid in the reaction system, and is a compound stably present in the absence of acid. These compounds accelerate the reaction progressively due to the increase of at least one acid in one reaction. However, since the generated acid itself undergoes self-decomposition, the intensity of the acid generated here is the acid dissociation constant, pKa 3 or less, and particularly preferably 2 or less.

Specific examples of the acid proliferating agent include the compounds described in paragraphs 0203 to 023 of JP-A No. 10-1508, paragraphs 0016 to 0055 of JP-A No. 10-282642, and JP-A No. 9-512498, page 39 12th line to 47th page 2nd line.

Examples of the acid growth agent that can be used in the present invention include acids having a pKa of 3 or less such as dichloroacetic acid, trichloroacetic acid, methanesulfonic acid, benzenesulfonic acid, trifluoromethanesulfonic acid, phenylphosphonic acid, etc., . &Lt; / RTI &gt;

The content of the acid proliferating agent in the resin composition is preferably from 10 to 1,000 parts by mass based on 100 parts by mass of the (E) photoacid generator from the viewpoint of dissolution contrast between the exposed portion and the unexposed portion, and preferably from 20 to 500 parts by mass More preferable.

(Method for producing positive-type photosensitive resin composition)

The process for producing the positive photosensitive resin composition of the present invention is not particularly limited, but may be a process comprising the steps of: (A) an inorganic particle; (B) a graft copolymer having a constitutional unit represented by any one of formulas (1) (A-1) a structural unit having an acid and / or a thermal cleavable group and (a-2) a structural unit having a crosslinking group (a-1) (Component E), and a step of adding a photoacid generator.

Since the component B also functions as a dispersant for the inorganic particles, it is preferable to mix the components A to C in advance to prepare a dispersion.

The mixing order of the components A to C is not particularly limited and three kinds may be mixed at the same time, and two kinds may be mixed first and the other one may be added thereto. It is also possible to combine the component A and the solvent, or to mix the component B and the solvent.

Examples of the solvent used in the preparation of the dispersion include, in addition to the above-mentioned (Component C) solvent, 1-propanol, 2-propanol, 1-butanol, 2-butanol, , Alcohols such as 2-pentanol, 3-pentanol, 3-methyl-1-butanol, 2-methyl-2-butanol, neopentanol, cyclopentanol, 1-hexanol and cyclohexanol have.

These solvents may be used alone or in combination of two or more.

The mixing means of the components A to E and other components are not particularly limited, but they are 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, .

When the dispersion is prepared in advance using the inorganic particles, the component B and the solvent, the content of the component B in the total solid content of the dispersion is preferably in the range of 0.1 to 50 mass% from the viewpoints of dispersion and dispersion stability , More preferably from 5 to 40 mass%, and still more preferably from 10 to 30 mass%.

The addition of the component D and the component E is not particularly limited. For example, the component D and the component E may be added to the dispersion simultaneously or sequentially, and the components D and E may be mixed with the solvent, It may be added to the dispersion.

The mixing timing of the components other than the components A to E is not particularly limited and may be mixed at the stage of the dispersion or may be mixed after the preparation. However, the dispersion is preferably mixed after the preparation .

(Production method of cured product)

The method for producing the cured product of the present invention is not particularly limited as long as it is a method for producing a cured product using the positive photosensitive resin composition of the present invention, but it is preferable that the method includes at least steps (a) to (c) in this order. 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 a film-shaped cured product such as a method including the following steps (a) to (c) , Or a patterned cured product as described later.

(a) a coating step of applying the positive photosensitive resin composition of the present invention onto a substrate

(b) a solvent removing step of removing the solvent from the applied resin composition

(c) a heat treatment step of heat-treating the resin composition from which the solvent has been removed

Each step will be described below in order.

<Coating Process [Process (a)]>

The method for producing the cured product of the present invention preferably includes (a) an application step of applying the positive photosensitive resin composition of the present invention onto a substrate.

In the step (a), it is preferable that a desired dry film is formed by applying the positive photosensitive resin composition of the present invention to a predetermined substrate and removing the solvent by reduced pressure and / or heating (prebaking).

Examples of the substrate material 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, Coated glass; Organic films such as polyimide and polyester; Metal, semiconductor, and any substrate containing a patterning region of an insulating material, but are not limited thereto. Optionally, a baking step may be performed on the substrate to remove absorbed moisture prior to application of the resin composition. The method of applying the coating liquid to the substrate is not particularly limited, and for example, slit coat method, spray method, roll coat method, spin coating method and the like can be used. In the case of a large substrate, the slit coat method is preferable. Here, a large substrate means a substrate having a size of 1 m or more and 5 m or less in each side.

<Solvent removal step [Step (b)]>

The method for producing the cured product of the present invention preferably includes a solvent removing step of (b) removing the solvent from the applied resin composition.

In the step (b), it is preferable that the solvent is removed from the applied film by depressurization (bubbling) and / or heating to form a dry film on the substrate. The heating conditions are preferably about 70 to 120 DEG C for about 30 to about 300 seconds.

The method for producing a resin pattern of the present invention is preferably used for manufacturing a thick film having a thickness of 4 mu m or more after removal of a solvent since the shape controllability is good. The film thickness after removing the solvent is preferably 4 to 500 mu m, more preferably 4 to 100 mu m.

<Heat Treatment Process [Step (c)]>

The method for producing a cured product of the present invention preferably includes a heat treatment step (baking step) for heat-treating the resin composition from which the solvent has been removed. The cured film can be formed by heat treatment.

The heat treatment temperature (baking temperature) is preferably 180 to 250 占 폚, and the heat treatment time is preferably 30 to 150 minutes.

For example, it is possible to use, as the component D, (a-1-1) a monomer having a carboxyl group or a phenolic hydroxyl group protected with an acid-decomposable group and (a-2-1) a monomer unit having an epoxy group and / or an oxetanyl group When a polymer is used, a curing film is formed by thermally decomposing an acid-decomposable group in the monomer unit (a-1-1) in the above-mentioned heat treatment step to produce a carboxyl group or a phenolic hydroxyl group and crosslinking with an epoxy group and / or an oxetanyl group .

When (Component F) a thermal cross-linking agent is used, it is preferable that the thermal cross-linking agent (Component F) is also thermally crosslinked in the heat-treatment step.

(Resin pattern production method)

The method for producing a resin pattern of the present invention is not particularly limited as long as it is a method for producing a resin pattern using the positive photosensitive resin composition of the present invention, but it is preferable that the method includes at least steps (1) to (5) in this order.

(1) A coating process for applying the positive photosensitive resin composition of the present invention onto a substrate

(2) a solvent removing step of removing the solvent from the applied resin composition

(3) an exposure step of exposing the resin composition from which the solvent has been removed to a pattern shape by an actinic ray

(4) a developing step of developing the exposed resin composition with an aqueous developing solution

(5) Heat treatment process for heat-treating the developed resin composition

Each step will be described below in order.

<Coating Process [Step (1)]>

The resin pattern production method of the present invention preferably includes (1) a coating step of applying the positive photosensitive resin composition of the present invention onto a substrate.

Step (1) is a step similar to that of step (a), and the same is true of preferred embodiments.

&Lt; Solvent removal step [Step (2)] >

The resin pattern production method of the present invention preferably includes a solvent removal step of (2) removing the solvent from the applied resin composition.

Step (2) is a step similar to the step (b), and the same is true for preferred embodiments.

&Lt; Exposure Step (Step (3)) >

The resin pattern production method of the present invention preferably includes an exposure step of exposing the resin composition from which the solvent has been removed to a pattern shape by an actinic ray.

In step (3), the substrate provided with the dry coating film is irradiated with an actinic ray of a predetermined pattern. The exposure may be performed through a mask, or a predetermined pattern may be directly drawn.

As the active light ray, an active ray having a wavelength of 300 nm or more and 450 nm or less can be preferably used. A low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a chemical lamp, a laser generator, an LED light source, and the like can be used for exposure by an actinic ray.

When a mercury lamp is used, an actinic ray having a wavelength of g-line (436 nm), i-line (365 nm) and h-line (405 nm) can be preferably used. The mercury lamp is preferable in that it is suitable for exposure of a large area as compared with a laser.

When a laser is used, various lasers can be used without any limitations by appropriately selecting the wavelength. For example, in a solid-state (YAG) laser, 343 nm and 355 nm are used, and in an excimer laser, 351 nm (XeF) is used, and in a semiconductor laser, 375 nm and 405 nm are used. Of these, 355 nm or 405 nm is more preferable in view of stability and cost. The laser can be irradiated to the coating film once or plural times.

The laser is preferable in that it is easy to narrow the focus as compared with a mercury lamp, and a mask for pattern formation in the exposure process is unnecessary, thereby reducing the cost.

Examples of the exposure apparatus that can be used in the present invention include, but are not limited to, commercially available products such as those available from Callisto (manufactured by V Technology) or AEGIS (manufactured by V Technology) or DF2200G (manufactured by Dainippon Screen Shoji Co., ] Can be used. Apparatuses other than those described above are also preferably used.

If necessary, the irradiation light can be adjusted through a spectral filter such as a long wavelength cut filter, a short wavelength cut filter, or a band pass filter.

After the exposure process, PEB (post-exposure heat treatment) can be performed before the development process as needed. The temperature at which PEB is carried out is preferably 30 占 폚 to 130 占 폚, more preferably 40 占 폚 to 110 占 폚, and particularly preferably 50 占 폚 to 90 占 폚.

<Development Process [Step (4)]>

The resin pattern production method of the present invention preferably includes (4) a developing step of developing the exposed resin composition by an aqueous developing solution.

In step (4), development is carried out using an aqueous developer.

As the aqueous developer, an alkaline developer is preferred. Examples of the basic compound that can be used for the alkaline developer include alkali metal hydroxide such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; Alkali metal carbonates such as sodium carbonate and potassium carbonate; Alkali metal bicarbonates such as sodium bicarbonate and potassium bicarbonate; Ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline hydroxide; An aqueous solution of sodium silicate, sodium metasilicate or the like can be used. An aqueous solution in which an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant is added to the aqueous alkaline solution may be used as a developer.

The pH of the developing solution is preferably 10.0 to 14.0.

The developing time is preferably 30 to 180 seconds, and the developing method may be any of a liquid filling method, a dipping method, and a shower method. After the development, it is preferable to carry out the water washing for 10 to 90 seconds to form a desired pattern.

The method for producing a resin pattern of the present invention may include a re-exposure step of re-exposing a substrate on which a pattern is formed between steps (4) and (5) by an actinic ray, but preferably not.

The exposure in the re-exposure step may be performed by the same means as in the exposure step, but in the re-exposure step, it is preferable to perform the entire exposure on the side where the resin composition film of the substrate is formed.

The preferable exposure amount of the re-exposure process is 100 to 1,000 mJ / cm &lt; 2 &gt;.

<Heat Treatment Process [Step (5)]>

The resin pattern production method of the present invention preferably includes a heat treatment step (baking step) for heat-treating the developed resin composition. The cured film can be formed by heat treatment.

Step (5) is a step similar to that of the step (c) except that the resin composition from which the solvent has been removed and the developed resin composition after the step (4) is used is the same as the preferred embodiment.

(Transfer material)

The positive photosensitive resin composition of the present invention can be preferably used as a transferring material. Specifically, it can be suitably used as a transfer material for use, for example, by transferring a resin composition provided on a branching material onto a substrate of a display device or a semiconductor substrate.

When the positive photosensitive resin composition of the present invention is used as a transfer material to form a resin pattern, the resin pattern production method of the present invention preferably includes the following steps (1 ') to (6') in this order .

(1 ') A coating process for applying the positive photosensitive resin composition of the present invention onto a support material

(2 ') a solvent removing step for removing the solvent from the applied resin composition

(3 ') Step of transferring the resin composition from which the solvent has been removed to a substrate (permanent support)

(4 ') an exposure process for exposing the transferred resin composition to a pattern by an actinic ray

(5 ') a developing step of developing the exposed resin composition with an aqueous developing solution

(6 ') Heat treatment process for heat-treating the developed resin composition

&Lt; Coating Process [Step (1 ')]

The resin pattern production method of the present invention preferably comprises (1 ') a coating step of applying the positive photosensitive resin composition of the present invention onto a substrate.

The step (1 ') is a step similar to that of the step (a) except that the substrate shown below is used in place of the substrate, and the preferred embodiment is also the same.

As the branching material, known materials such as polyester and polystyrene can be used. Among them, biaxially stretched polyethylene terephthalate is preferable from the viewpoints of cost, heat resistance and dimensional stability.

The thickness of the branched body is preferably 15 to 200 mu m, more preferably 30 to 150 mu m.

&Lt; Solvent removal step [Step (2 ')]

The resin pattern production method of the present invention preferably includes a solvent removal step of removing the solvent from the resin composition (2 ').

The step (2 ') is a step similar to the step (b), and the preferable mode is the same.

&Lt; Transcription step [Step (3 ')]

The resin pattern production method of the present invention preferably includes a step of transferring (3 ') the resin composition from which the solvent has been removed to a substrate (permanent support).

The transferring 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 branching agent from the resin composition adhered 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 hot pressing on a heated and / or pressurized roller or flat plate.

Specifically, the laminator and the lamination method disclosed in Japanese Patent Application Laid-Open Nos. 7-110575, 11-77942, 2000-334836, and 2002-148794 However, it is preferable to use the method described in Japanese Patent Application Laid-Open No. 7-110575 from the viewpoint of low water.

The method of removing branch lags is not particularly limited, but it can be removed, for example, by bringing a pressure-sensitive adhesive roller having an adhesive layer into contact with the branch support and peeling the branch support from the resin composition adhered to the substrate. The delamination of the branch lug can be peeled by grasping the end portion of the branch lug protruded from the substrate separated by the continuous peeling or the single wafer laminating method.

The method of peeling the branched body is preferably a method described in Japanese Patent Application Laid-Open No. 2006-297879 for continuous peeling, and a method described in Japanese Patent Application Laid-Open No. 2007-320678 for sheet laminating.

&Lt; Exposure Step (Step (4 ')]

The method for producing a resin pattern of the present invention preferably includes an exposure step of exposing the transferred resin composition to a pattern shape by an actinic ray (4 ').

The step (4 ') is a step similar to the step (3) except that the resin composition from which the solvent has been removed is used in place of the transferred resin composition obtained through the step (3').

&Lt; Development process (step (5 ')]

The resin pattern manufacturing method of the present invention preferably includes a developing step (5 ') for developing the exposed resin composition by an aqueous developing solution.

The step (5 ') is a step similar to the step (4), and the preferable mode is the same.

&Lt; Heat treatment step [Step (6 ')]

The resin pattern production method of the present invention preferably includes a heat treatment step (6 ') for heat-treating the developed resin composition. The cured film can be formed by heat treatment.

The step (6 ') is a step similar to the step (5), and the preferable mode is the same.

As a resin pattern production method for forming a resin pattern by using the resin composition of the present invention as a transfer material, Japanese Patent Application Laid-Open No. 2010-72589 can also be referred to.

(Cured product, optical member)

The cured product of the present invention is not particularly limited as long as it is a cured product of the positive photosensitive resin composition of the present invention, but is preferably a cured product produced by the method of producing a cured product of the present invention or the method of producing a resin pattern.

Further, the cured product of the present invention can be preferably used as an optical member such as a microlens, an optical waveguide, or an antireflection film. The cured product of the present invention can also be preferably used as a member for reducing visibility of a wiring electrode used in a touch panel. Among them, micro lenses can be particularly preferably used.

Example

EXAMPLES Next, the present invention will be described in more detail with reference to Examples. However, the present invention is not limited to these examples. Unless specifically stated, &quot; part &quot; and &quot;% &quot; are based on mass.

<Preparation of dispersion>

The dispersion was mixed with 17,000 parts by mass of zirconia beads (0.2 mm?) And dispersed for 10 hours using a paint shaker. Zirconia beads (0.2 mm?) Were separated by filtration to obtain dispersions D1 to D18, respectively.

Further, the dispersing agent was adjusted by a solvent so that the amount of the solid component became equal.

- Titanium dioxide [trade name: TTO-51 (C), average primary particle diameter: 10 to 30 nm, manufactured by Ishihara Sangyo Co., Ltd.): 1,880 parts

Dispersant (solid content): 660 parts

Solvent PGMEA (propylene glycol monomethyl ether acetate): 4,970 parts

Table 1 shows the initial viscosity of the dispersions D1 to D18 obtained as described above and the viscosity after storage at room temperature (25 DEG C) for 1 week.

The lower the difference between the initial viscosity and the viscosity after storage for one week at room temperature is, the better the storage stability is.

The dispersants listed in Table 1 are as follows. In addition, the copolymerization ratio described in the lower right of parentheses [] of the compounds 1 to 6 is a mass% ratio. In addition, the number shown on the lower right of the parentheses () indicates the number of repetitions.

TTO-55 (C): titanium dioxide, manufactured by Ishihara Sangyo KK, average primary particle diameter: 30 to 50 nm

RC-100: zirconium dioxide, manufactured by Dai-ichi Kigenso Kagaku Corp., D ₅₀ : 1.5 to 4 탆

Compound 1: The following compound, Mw = 20,000

Compound 2: The following compound, Mw = 20,000

Compound 3: The following compound, Mw = 20,000

Compound 4: The following compound, Mw = 20,000

Compound 5: The following compound, Mw = 20,000

Compound 6: The following compound, Mw = 20,000

DISPERBYK-161 (manufactured by Big Chemical)

DISPERBYK-164 (made by Big Chemical)

DISPERBYK-180 (manufactured by Big Chemical)

SOLPLUS D540 (manufactured by Nippon Lubrizol Corporation)

&Lt; Synthesis of Polymer &

In the following Synthesis Examples, the following abbreviations respectively represent the following compounds.

V-601: Dimethyl-2,2'-azobis (2-methylpropionate)

PGMEA: Propylene glycol monomethyl ether acetate

&Lt; Synthesis of Polymer P1 &

Methacrylic acid (0.40 molar equivalent), methacrylic acid (0.20 molar equivalent), and methacrylic acid (3-ethyloxetan-3-yl) methyl methacrylate (0.40 molar equivalent) , And propylene glycol monomethyl ether acetate (PGMEA) (120 parts) was heated to 70 占 폚 under a nitrogen stream. While stirring this mixture solution, a radical polymerization initiator V-601: dimethyl-2,2'-azobis (2-methylpropionate), 12.0 parts of Wako Pure Chemical Industries, Ltd. and PGMEA (80 parts) Was added dropwise over 3.5 hours. After completion of the dropwise addition, the reaction was carried out at 70 DEG C for 2 hours to obtain a PGMEA solution of the polymer P1. Further, PGMEA was added to adjust the solid content concentration to 40 mass%.

The polymer P1 thus obtained had a weight average molecular weight (Mw) of 15,000 as measured by gel permeation chromatography (GPC).

&Lt; Synthesis of polymers P2 to P6 >

Except that the respective monomers used in the synthesis of the polymer P1 were changed to the monomers forming the respective monomer units described in Table 2 and the amounts of the monomers forming the respective monomer units were changed to those described in Table 1, Polymers P2 to P6 were synthesized, respectively. The addition amount of the radical polymerization initiator V-601 was adjusted so as to have the molecular weights shown in Table 2, respectively.

The amounts shown in Table 2 are molar ratios and show the copolymerization ratios of the respective monomer-derived constituent units described in the category column. In Table 2, "-" indicates that the monomer unit is not used.

The abbreviations in Table 2 are as follows.

MAEVE: 1-ethoxyethyl methacrylate

MATHF: tetrahydrofuran-2-yl methacrylate

OXE-30: methacrylic acid (3-ethyloxetan-3-yl) methyl [manufactured by Osaka Yuki Kagaku Kogyo Co., Ltd.]

MAA: methacrylic acid

BzMA: Benzyl methacrylate

HEMA: 2-hydroxyethyl methacrylate

GMA: glycidyl methacrylate

(Preparation of photosensitive resin composition)

The resulting solution was mixed with the following composition to prepare a homogeneous solution, which was then filtered through a polyethylene filter having a pore size of 0.2 μm to prepare a photosensitive resin composition of Example 1.

(Example 1)

Propylene glycol monomethyl ether acetate: 140 parts

0.5% PGMEA solution of 1,5-diazabicyclo [4.3.0] -5-nonene: 18 parts

· 0.2% PGMEA solution of triphenylimidazole: 4 parts

Polymer P1: 223 parts

? - (p-toluenesulfonyloxyimino) phenylacetonitrile: 2 parts

· JER157S65 [manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 200 to 220 g / eq]: 5 parts

3-glycidoxypropyltrimethoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.): 3 parts

2.0% PGMEA solution of the following compound W-3: 5 parts

Dispersion D1: 600 parts

(Evaluation of coating surface shape)

The obtained photosensitive resin composition was coated on a glass substrate (trade name: XG, Corning) having a size of 100 mm x 100 mm with a spin coater so as to have a film thickness of 1.0 탆 and dried (prebaked) on a hot plate at 90 캜 for 120 seconds . The state of the coated surface at this time was observed with a naked eye and an optical microscope, and evaluated according to the following evaluation criteria.

1: It was a clear coated surface free from opacity and crack (crack).

2: It was a slightly turbid coating.

3: The surface of the coating was cloudy.

4: White turbidity was seen on the coated surface, and a crack (crack) was also observed.

(Evaluation of transmittance)

The obtained photosensitive resin composition was coated on a glass substrate (trade name: XG, Corning) having a size of 100 mm x 100 mm with a spin coater so as to have a film thickness of 1.0 탆 and dried (prebaked) on a hot plate at 90 캜 for 120 seconds . The coating film was subjected to heat treatment (post baking) in an oven at 230 캜 for 30 minutes, and the post-baking spectra were measured with MCPD-3000 manufactured by Otsuka Denshi Co., Ltd., and the transmittance of 400 nm was measured according to the following evaluation criteria I appreciated.

The transmittance at 1: 400 nm was 90% or more.

2: The transmittance of 400 nm was 85% or more and less than 90%.

3: The transmittance of 400 nm was less than 85%.

(Evaluation of resolution)

The obtained photosensitive resin composition was coated on a glass substrate (trade name: XG, Corning) having a size of 100 mm x 100 mm with a spin coater so as to have a film thickness of 1.0 탆 and dried (prebaked) on a hot plate at 90 캜 for 120 seconds .

Subsequently, exposure was carried out using a ghi-ray hybrid type exposure apparatus through a mask having a 1% to 60% line-and-space gradient of 1: 1 at an illumination intensity of 20 mW / cm 2 and 200 mJ / cm 2.

Subsequently, development was carried out with a 0.4% tetramethylammonium hydroxide aqueous solution at 23 占 폚 for 10 seconds by dip filling method, and further rinsed with ultrapure water for 10 seconds. Subsequently, a pattern was obtained by heating at 220 DEG C for 30 minutes. This pattern was observed with an optical microscope.

This operation was started from the width of the line and space of the mask of 50 mu m, and the minimum width in which the pattern of the optimal exposure amount was clearly formed was defined as the resolution by narrowing the width by 5 mu m by 5 mu m until 10 mu m and by 1 mu m by 10 mu m or less.

1: Resolution was 10 탆 or less.

2: The resolution was more than 10 탆 and not more than 50 탆.

3: The pattern could not be formed at a line-and-space width of 50 mu m of the mask.

4: The entire film was peeled off.

In Examples 2 to 24 and Comparative Examples 1 to 24, the photosensitive resin composition was adjusted in the same manner as in Example 1 except that the dispersion and component B were changed to Table 3, and the shape of the applied surface, the transmittance and the resolution were evaluated.

Claims (12)

(Component A) An inorganic particle,
(Component B) A graft copolymer having a constitutional unit represented by any one of formulas (1) to (4)
(Component C) Solvent,
(Component D) a polymer having (a-1) a structural unit having an acid and / or a thermal eliminable group and (a-2) a structural unit having a crosslinking group, and
(Component E) a positive photo-sensitive resin composition.

In the formula (1) to equation ^{(4), X 1, X} 2, X 3, X 4 and X ⁵ each independently represents a hydrogen atom or a monovalent ^{organic, 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, n, m, p and q are each independently of 3-500 And j and k are each independently an integer of 2 to 8, The method according to claim 1,
Wherein the component A is a metal oxide particle. 3. The method of claim 2,
Wherein the component A is a titanium oxide particle or a zirconium oxide particle. 4. The method according to any one of claims 1 to 3,
And the component B is a graft copolymer further having a structural unit having a carboxylic acid group. 5. The method according to any one of claims 1 to 4,
(Component F) A positive type photosensitive resin composition, further comprising a heat crosslinking agent. 6. The method according to any one of claims 1 to 5,
And the acid value of the component D exceeds 50 mgKOH / g. 7. The method according to any one of claims 1 to 6,
And the component B has a weight average molecular weight of less than 25,000. 8. The method according to any one of claims 1 to 7,
Wherein the positive photosensitive resin composition is a resin composition for an optical member. Wherein at least the steps (a) to (c) are included in this order.
(a) a coating step of applying the positive-working photosensitive resin composition according to any one of claims 1 to 8 onto a substrate
(b) a solvent removing step of removing the solvent from the applied resin composition
(c) a heat treatment step of heat-treating the resin composition from which the solvent has been removed A method for producing a resin pattern, comprising at least steps (1) to (5) in this order.
(1) A coating process for applying the positive-working photosensitive resin composition according to any one of claims 1 to 8 onto a substrate
(2) a solvent removing step of removing the solvent from the applied resin composition
(3) an exposure step of exposing the resin composition from which the solvent has been removed to a pattern shape by an actinic ray
(4) a developing step of developing the exposed resin composition with an aqueous developing solution
(5) Heat treatment process for heat-treating the developed resin composition A cured product obtained by the process for producing a cured product according to claim 9 or the process for producing a resin pattern according to claim 10. An optical member characterized by being obtained by the process for producing a cured product according to claim 9 or the process for producing a resin pattern according to claim 10.