KR20140144168A - Positive type photosensitive resin composition, method for forming cured film, cured film, liquid crystal display device, and organic el display device - Google Patents

Abstract

Provided is a positive type photosensitive resin composition containing a resin (A) and a sensitive radiation acid generator (B), wherein the resin has 0.6-0.8 of an I/O value in which an inorganic value (I) is dived by an organic value (O) based on an inorganic concept map, and 5-110 mgKOH/g of an acid value. Also, the resin has an acid radical protected by an acid decomposable group, an acid radical, and a crosslinking radical.

Description

TECHNICAL FIELD [0001] The present invention relates to a positive type photosensitive resin composition, a method of forming a cured film, a cured film, a liquid crystal display, and an organic EL display device }

The present invention relates to a positive photosensitive resin composition, a method of forming a cured film, a cured film, a liquid crystal display, and an organic EL display.

In an organic EL display device, a liquid crystal display device or the like, a patterned interlayer insulating film is provided. In forming this interlayer insulating film, a photosensitive resin composition is widely used in that the number of steps for obtaining a required pattern shape is small, and furthermore, sufficient flatness is obtained. The interlayer insulating film in the display device is required to have high transparency in addition to the physical properties of a cured film excellent in insulating property, solvent resistance, heat resistance, and indium tin oxide (ITO) sputter suitability. For this reason, it has been attempted to use an acrylic resin having excellent transparency as a film forming component.

As such a photosensitive resin composition, for example, Patent Document 1 discloses a resin composition comprising a structural unit derived from a radical polymerizing compound having a functional group capable of reacting with a radical polymerizing (fluorinated) hydrocarbon, an unsaturated carboxylic acid and a carboxyl group to form a crosslinking , And a composition containing a radiation-sensitive acid generator (radiation-sensitive scattering agent) have been proposed.

Patent Document 2 proposes a composition containing a high molecular weight substance having an acetal structure and / or a ketal structure and an epoxy structure and having a polystyrene reduced weight average molecular weight of 2000 or more as measured by gel permeation chromatography and a specific radiolytic acid generator have.

Patent Document 3 discloses a high molecular weight compound having an acetal structure and / or a ketal structure and a t-butyl structure of carboxylic acid and having a weight average molecular weight of 2000 or more in terms of polystyrene measured by gel permeation chromatography and a compound having two or more epoxy groups in the molecule Have been proposed.

Patent Document 4 proposes a composition containing an alkali-soluble resin having a phenolic hydroxyl group and a radiation-sensitive acid generator.

Patent Document 5 discloses a resin composition containing a structural unit having a specific acid-cleavable group and a structural unit having a functional group capable of reacting with a carboxyl group to form a covalent bond and being alkali-insoluble or alkali-insoluble, A resin that becomes alkali soluble when dissociated, and a compound that generates an acid upon irradiation with an actinic ray or radiation.

On the other hand, as an optical system material of an optical system or an optical fiber connector of an on-chip color filter such as a facsimile, an electronic copying machine, or a solid-state image pickup element, a microlens having a lens diameter of about 3 to 100 m or a microlens array (arrays) are used.

In order to form the microlenses or microlens arrays, a method in which a resist pattern corresponding to a lens is formed and then subjected to a heat treatment to perform a melt flow so as to be used as a lens, or a method in which a lens pattern to be melted is used as a mask to dry- A method of transferring a lens shape, and the like are known. For forming the lens pattern, a photosensitive resin composition is widely used (see, for example, Patent Documents 6 and 7).

Japanese Patent Application Laid-Open No. 2005-248129 Japanese Patent Application Laid-Open No. 10-26829 Japanese Patent Application Laid-Open No. 2004-264623 Japanese Patent Application Laid-Open No. 2007-65488 Japanese Patent Application Laid-Open No. 2009-98616 Japanese Patent Application Laid-Open No. 6-18702 Japanese Patent Application Laid-Open No. 6-136239

When a cured film to be applied to an interlayer insulating film or the like is formed by the photosensitive resin composition, it is required that the generation of a residue at the time of development is suppressed in addition to high sensitivity, and that the surface of the cured film formed is smooth.

However, the conventional photosensitive resin composition does not satisfy all of sensitivity, restraint, and smoothness of the surface of the cured film, and a further improvement is demanded from the present state of the art.

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances in the prior art, and solves the following problems.

That is to say, an object of the present invention is to provide a positive photosensitive resin composition capable of forming a cured film having a high sensitivity, suppressing the occurrence of residues during development, and having a surface with excellent smoothness.

Another object of the present invention is to provide a method of forming a cured film by using the positive photosensitive resin composition of the present invention and a cured film formed by the method of forming the cured film and an interlayer insulating film using the cured film, And a liquid crystal display device and an organic EL display device provided with the cured film.

The above problem is solved by the following means.

The resin (A) contains an I / O value obtained by dividing an inorganic value (I) based on an organic conceptual diagram by an organic value (O), wherein the resin (A) Or more and 0.6 or more and 0.8 or less, an acid value of 5 mgKOH / g or more and 110 mgKOH / g or less, and having an acid group, an acid group and a crosslinkable group protected with an acid decomposable group.

<2> The positive photosensitive resin composition according to <1>, wherein the resin (A) is a resin having an I / O value of 0.6 or more and 0.8 or less and an acid value of 20 mgKOH / g or more and 70 mgKOH / g or less.

<3> The positive photosensitive resin composition according to <1> or <2>, wherein the acid group is a carboxyl group or a phenolic hydroxyl group.

<4> The positive photosensitive resin composition according to any one of <1> to <3>, wherein the acid group protected by the acid-decomposable group is a group which generates a carboxyl group or a phenolic hydroxyl group by the action of an acid.

<5> The positive photosensitive resin composition according to any one of <1> to <4>, wherein the acid group is a carboxyl group and the acid group protected by the acid-decomposable group generates a carboxyl group by the action of an acid.

<6> The positive photosensitive resin composition according to any one of <1> to <5>, wherein the crosslinking group is an epoxy group or an oxetanyl group.

<7> The resin composition according to <7>, wherein the resin (A) contains a structural unit derived from a radically polymerizable compound containing an acid group protected by an acid-decomposable group, a radical polymerizable compound containing an unsaturated carboxylic acid and an epoxy group or an oxetanyl group The positive photosensitive resin composition according to any one of < 1 > to &lt; 6 &gt;

<8> The positive photosensitive resin composition according to <7>, wherein the radically polymerizable compound containing an epoxy group or an oxetanyl group is a radically polymerizable compound containing an oxetanyl group.

<9> The resin composition according to <9>, wherein the resin (A) further contains a structural unit derived from at least one selected from the group consisting of a hydroxyl group-containing unsaturated carboxylic acid ester, an alicyclic structure-containing unsaturated carboxylic acid ester, styrene, Chain The positive photosensitive resin composition described in the above item <7> or <8>.

<10> The positive photosensitive resin composition according to any one of <1> to <9>, wherein the radiation-sensitive acid generator (B) is a compound having an oxime sulfonate group.

<11> The positive photosensitive resin composition according to any one of <1> to <10>, wherein the radiation-sensitive acid generator (B) is a compound represented by the following formula (OS-3).

In the general formula (OS-3), R ¹ represents an alkyl group, an aryl group or a heteroaryl group, and the plurality of R ^{2 s} present each independently represent a hydrogen atom, an alkyl group, an aryl group or a halogen atom, R ⁶ which may be present 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, m represents an integer of 0 to 6;

<12> The positive photosensitive resin composition according to any one of <1> to <6>, wherein the positive resist composition contains the resin (A) in a range of 60% by mass to 95% by mass, The positive photosensitive resin composition according to any one of &lt; 1 &gt; to &lt; 10 &gt;

<13> The positive photosensitive resin composition according to any one of <1> to <11>, further comprising a crosslinking agent.

<14> The positive photosensitive resin composition according to any one of <1> to <9>, wherein the positive resist composition contains the resin (A) in an amount of 40% by mass to 70% by mass, , And the crosslinking agent is contained in a range of 3% by mass to 40% by mass. The positive photosensitive resin composition according to &lt; 13 &gt;

<15> A cured film obtained by curing a positive photosensitive resin composition described in any one of <1> to <13> by applying at least one of light and heat.

(1) A positive photosensitive resin composition according to any one of the above items <1> to <13>

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

(3) an exposure step of exposing the positive photosensitive resin composition from which the solvent has been removed to active radiation,

(4) a developing step of developing the exposed positive photosensitive resin composition with an aqueous developing solution, and

(5) a post-baking step of thermally curing the developed positive photosensitive resin composition

To form a cured film.

<17> The method for forming a cured film according to <16>, wherein the developing step is performed after the exposure in the exposure step, but without the heat treatment.

<18> A cured film formed by the method for forming a cured film according to <16> or <17>.

<19> The cured film according to <15> or <18>, which is an interlayer insulating film.

<20> A liquid crystal display device comprising the cured film according to <15> or <18>.

<21> An organic EL display device comprising the cured film according to <15> or <18>.

According to the present invention, it is possible to provide a positive photosensitive resin composition capable of forming a cured film having a high sensitivity, suppressing the occurrence of residues during development, and having a surface with excellent smoothness.

According to the present invention, there is also provided a method of forming a cured film using the positive photosensitive resin composition of the present invention, a cured film formed by the method of forming the cured film, and an interlayer insulating film using the cured film, A liquid crystal display device having the cured film and an organic EL display device can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a structural conceptual diagram showing an example of an organic EL display device using the photosensitive resin composition of the present invention. Fig.
Fig. 2 shows a structural conceptual diagram of an example of a liquid crystal display device using the photosensitive resin composition of the present invention.

&Lt; Positive photosensitive resin composition >

Hereinafter, the positive photosensitive resin composition of the present invention (hereinafter referred to as "photosensitive resin composition" as appropriate) will be described in detail.

The photosensitive resin composition of the present invention contains a resin (A) and a radiation-sensitive acid generator (B) (hereinafter, appropriately referred to as an "acid generator") and the resin (A) An acid value, an acid value, and a crosslinkable group protected by an acid-decomposable group, and an acid value (I) divided by an organic value (O) is 0.6 or more and 0.8 or less, an acid value is 5 mgKOH / g or more and 110 mgKOH / g or less, (Hereinafter referred to as &quot; specific resin &quot; as appropriate).

The photosensitive resin composition of the present invention has excellent sensitivity by containing a specific resin and an acid generator. In addition, the photosensitive resin composition of the present invention can form a cured film having a surface with excellent smoothness while suppressing the occurrence of residue at the time of development.

In the present invention, the term &quot; residue &quot; means a residual film existing on the peripheral edge of the patterned cured film end portion when the patterned cured film is formed using the photosensitive resin composition.

In addition, the smoothness of the surface of the cured film is determined by the surface roughness (Ra) of the surface of the cured film as its index, and may be referred to as &quot; surface roughness &quot; hereinafter. In the present specification, the surface roughness (Ra) of the surface of the cured film is a value measured by a stylus type surface roughness meter "P10" (manufactured by Tencor).

The cured film obtained by the photosensitive resin composition of the present invention can be suitably used as an interlayer insulating film, a planarizing film, and the like provided in a liquid crystal display device or an organic EL display device.

When the flatness of the insulating film included in the liquid crystal display device or the organic EL display device is lowered, the electric resistance of the ITO electrode stacked on the insulating film increases, or when the adverse effect that the liquid crystal alignment in the liquid crystal layer stacked on the insulating film is disturbed . In this respect, the cured film obtained by the photosensitive resin composition of the present invention is excellent in the smoothness of the surface (there is no surface roughness), and the occurrence of such harmful effects is effectively suppressed.

Further, since the photosensitive composition of the present invention is also suppressed from the occurrence of residues during development, it is possible to form a cured film in a pattern of a good shape. This is particularly useful when, for example, a contact hole or the like is formed.

The photosensitive resin composition of the present invention is preferably a chemically amplified positive photosensitive resin composition (chemically amplified positive photosensitive resin composition).

Hereinafter, specific resins and acid generators which are characteristic components constituting the photosensitive resin composition of the present invention will be described.

In the notation of the group (atomic group) in the present specification, the notation in which substitution and non-substitution are not described includes those having a substituent and having 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).

The method for introducing the structural unit contained in the copolymer used in the present invention may be a polymerization method or a polymer reaction method. In the polymerization method, monomers containing a predetermined functional group are synthesized in advance, and then these monomers are copolymerized. In the polymer reaction method, a necessary functional group is introduced into the structural unit by using a reactive group contained in the structural unit of the obtained copolymer after the polymerization reaction. Examples of the functional group include a protecting group for protecting the acid group such as a carboxyl group or a phenolic hydroxyl group and decomposing it in the presence of a strong acid, a crosslinking group such as an epoxy group or an oxetanyl group, or an alkaline group such as a phenolic hydroxyl group or a carboxy group And a soluble group (acid group).

(Specific resin)

The specific resin contained in the photosensitive resin composition of the present invention has an I / O value of 0.6 or more and 0.8 or less, which is obtained by dividing the inorganic value (I) based on the organic concept diagram by the organic value (O), and the acid value is 5 mgKOH / g or more and 110 mgKOH / g or less, and further has an acid group, an acid group, and a crosslinkable group protected by an acid-decomposable group.

The specific resin may be contained in only one kind in the photosensitive resin composition, or two or more kinds may be used in combination.

The present inventors have focused on the relationship between the I / O value and the acid value of the resin contained in the photosensitive resin composition and the specific partial structure possessed by the resin to show the I / O value and the acid value within a specific range, The inclusion of a specific resin which is a resin having an acid group, an acid group and a crosslinkable group protected by a group achieves both a high sensitivity of the photosensitive resin composition, suppression of generation of residue at the time of development, and smoothness of the surface of the formed cured film It can be done.

The specific resin preferably has an I / O value of not less than 0.6 and not more than 0.8 and an acid value of not less than 5 mgKOH / g and not more than 110 mgKOH / g, and an I / O value of not less than 0.6 and not more than 0.8 and an acid value of not less than 20 mgKOH / g and not less than 70 mgKOH / g Or less.

Here, the I / O value is a value obtained by treating the polarity of various organic compounds, which may be referred to as an inorganic value / organic value, in an organic concept, and is one of the functional group contributing methods for setting parameters in each functional group.

As for the I / O value, an organic concept (Koda Yoshio, Sankyo Shotpan (1984)); KUMAMOTO PHARMACEUTICAL BULLETIN, No. 1, Nos. 1-16 (1954); Area of Chemistry, Vol. 11, No. 10, pp. 719-725 (1957); Fragrance journal, No. 34, lines 97 to 111 (1979); Fragrance Journal, No. 50, pp. 79-82 (1981); And the like.

The concept of the I / O value is that the property of a compound is divided into an organic group exhibiting covalent bonding property and an inorganic group exhibiting ionic bonding property and being positioned at one point on the Cartesian coordinates denoting all organic compounds as an organic axis and an inorganic axis Is designated.

The inorganic value is obtained by quantifying the influence of various substituents or bonds of the organic compound on the boiling point with reference to the hydroxyl group. Concretely, when the distance between the boiling curve of the straight chain alcohol and the boiling curve of the linear paraffin is about 100 ° C, the influence of one hydroxyl group is set to 100 as a numerical value. Based on this numerical value, various substituents Or a value obtained by quantifying the influence on the boiling point of various bonds or the like is an inorganic value of a substituent group possessed by the organic compound. For example, the inorganic value of the -COOH group is 150, and the inorganic value of the double bond is 2. Therefore, the inorganic value of any kind of organic compound means the sum of inorganic values such as various substituents and bonds possessed by the compound.

The organic value is determined based on the influence of the carbon atom representing the methylene group on the boiling point, with the methylene group in the molecule as a unit. That is, since the average value of the boiling point increase due to the addition of one carbon at about 5 to 10 carbon atoms of the linear saturated hydrocarbon compound is 20 ° C, the organic value of one carbon atom is set at 20 based on this, The value obtained by quantifying the influence on the boiling point of the bond or the like is an organic value. For example, the organic value of the nitro group (-NO ₂ ) is 70.

The closer to 0 the I / O value is, the more non-polar (organic hydrophobic and hydrophobic) organic compound is, and the larger the value, the more polar (hydrophilic, highly inorganic) organic compound.

Hereinafter, an example of a method of calculating the I / O value will be described.

The I / O value of the methacrylic acid / methyl methacrylate / styrene copolymer (copolymerization molar ratio: 2/5/3) was calculated by the following method by using inorganic and organic values of the copolymer, .

I / O value = (inorganic value of copolymer) / (organic value of copolymer)

The inorganic value of the copolymer is preferably such that an inorganic value of (methacrylic acid) x (a molar ratio of methacrylic acid), (an inorganic value of methyl methacrylate) x (a molar ratio of methyl methacrylate) (Styrene value) x (molar ratio of styrene).

Since the methacrylic acid has one carboxyl group, the methacrylic acid has one ester group, and the styrene has one aromatic ring, the inorganic value of the methacrylic acid is 150 (inorganic value of the carboxyl group) x 1 (Inorganic number of ester group) x 1 (number of ester groups) = 60, and the inorganic value of styrene is 15 (inorganic value of aromatic ring) x 1 (number of aromatic rings) = 15.

Accordingly, the inorganic value of the copolymer is 645 by the ratio of 150 x 2 (molar ratio of methacrylic acid) + 60 x 5 (molar ratio of methyl methacrylate) + 15 x 3 (molar ratio of styrene).

The organic value of the copolymer was determined from the following formula: (organic value of methacrylic acid) x (molar ratio of methacrylic acid), (organic value of methyl methacrylate) x (molar ratio of methyl methacrylate) Value) x (molar ratio of styrene).

Since methacrylic acid has 4 carbon atoms, methyl methacrylate has 5 carbon atoms, and styrene has 8 carbon atoms, the organic value of the methacrylic acid is 20 (organic value of carbon atoms) x The organic value of the styrene is 20 (the number of carbon atoms) = 80, the organic value of the methyl methacrylate is 20 (the organic value of the carbon atoms) x 5 (the number of carbon atoms) = 100, Value) x 8 (number of carbon atoms) = 160.

Therefore, the organic value of the copolymer is 1140 by 80 × 2 (molar ratio of methacrylic acid) + 100 × 5 (molar ratio of methyl methacrylate) + 160 × 3 (molar ratio of styrene).

As described above, the I / O value of the methacrylic acid / methyl methacrylate / styrene copolymer is 645 (inorganic value of the copolymer) / 1140 (organic value of the copolymer) = 0.566. As such, there is a close relationship between the I / O value and the composition ratio of the monomers constituting the resin.

The I / O value in the present specification is a value calculated by the above-described calculation method.

In the present specification, the acid value is a value obtained by dissolving a specific resin in a solvent and titrating with a 0.1 N NaOH solution.

When the photosensitive resin composition contains one kind of a specific resin, the I / O value and the acid value of the one kind of the specific resin are taken as the I / O value and the acid value of the specific resin. When the photosensitive resin composition contains two or more kinds of specific resins, the I / O value and the acid value of each specific resin are multiplied by the mass fractions to obtain a sum value.

As a method for controlling the I / O value represented by a specific resin, for example, the I / O value can be increased by increasing the ratio of groups having a large inorganic value such as a hydroxyethyl group or a hydroxypropyl group in the resin, The I / O value can be lowered by increasing the proportion of groups having a large organic value such as a chloropentanyl group or a dodecyl group in the resin.

As a method for controlling the acid value of a specific resin, for example, the acid value can be increased by increasing the proportion of the acid group such as a carboxyl group and a phenolic hydroxyl group, and the acid value can be lowered by decreasing the proportion of the acid group in the resin.

Hereinafter, the acid groups, acid groups, and crosslinkable groups protected with acid decomposable groups, which are partial structures possessed by specific resins, will be described in detail.

[Acid group protected with an acid-decomposable group]

The specific resin has an acid group protected by an acid-decomposable group.

The acid group protected by the acid-decomposable group of the specific resin is a compound having a partial structure represented by the following general formula (Ia) which generates a carboxy group by an acid and a partial structure represented by the general formula (Ib) (Hereinafter referred to as "structural unit (a1)" as appropriate) having a structure represented by the following general formula (IIa) and a partial structure represented by the following general formula (IIa) (A2) having at least one of the partial structures represented by the following general formula (IIb) for producing a phenolic hydroxyl group (hereinafter referred to as "structural unit (a2)" as appropriate) desirable.

In the general formulas (Ia) to (IIb), R ¹ represents an alkyl group or a cycloalkyl group, and R ² represents an alkyl group. R ³ represents a tertiary alkyl group, a 2-tetrahydropyranyl group or a 2-tetrahydrofuranyl group, R ⁴ represents a tertiary alkyl group, a tert-butoxycarbonyl group, a 2-tetrahydropyranyl group, Lt; / RTI &gt; Ar ¹ and Ar ² represent an aryl group, and the broken line portion represents a bonding site with another structure.

The acid group protected by the acid-decomposable group of the specific resin preferably contains at least one of the structural unit (a1) and the structural unit (a2), and it is preferable that the structural unit (a1) May be contained.

Among them, the partial structure represented by the general formula (Ia) or the partial structure represented by the general formula (Ib) is preferable, and the partial structure represented by the general formula (Ia) is more preferable.

In the present invention, the specific resin is preferably a resin that is alkali-insoluble and becomes alkali-soluble when the acid-decomposable group decomposes.

The term "alkali solubility" in the present invention means that the coating film (thickness: 3 μm) of the compound (resin) formed by applying the solution of the compound (resin) on a substrate and heating the same at 90 ° C. for 2 minutes at 23 ° C. Means that the dissolution rate of the compound (resin) in a 0.4% aqueous solution of tetramethylammonium hydroxide in the aqueous solution is 0.01 m / sec or more. The term "alkali insoluble" means that the solution of the compound Refers to a dissolution rate of a coating film (thickness 3 占 퐉) of the compound (resin) formed by heating in an aqueous solution of 0.4% tetramethylammonium hydroxide at 23 占 폚 of less than 0.01 占 퐉 / second.

The alkali dissolution rate of the specific resin in the present invention is more preferably less than 0.005 탆 / second. When the acid-decomposable group of the specific resin is decomposed, the alkali dissolution rate is preferably 0.05 m / sec or more.

The specific resin in the present invention is preferably an acrylic polymer.

The "acrylic polymer" in the present invention is an addition polymerizable type resin and is a polymer containing a structural unit derived from (meth) acrylic acid and / or an ester thereof, and is a polymer containing a structural unit derived from (meth) acrylic acid and / A structural unit other than the structural unit, for example, a structural unit derived from a styrene or a structural unit derived from a vinyl compound.

The specific resin preferably has a structural unit derived from (meth) acrylic acid and / or an ester thereof in an amount of preferably 50 mol% or more, more preferably 80 mol% or more, It is particularly preferable that the polymer is a polymer comprising only structural units derived from acrylic acid and / or an ester thereof.

The "structural unit derived from (meth) acrylic acid and / or its ester" is also referred to as "acrylic structural unit". Further, (meth) acrylic acid generally refers to methacrylic acid and acrylic acid.

<< Structural unit (a1) >>

(A1) having at least one of a partial structure represented by the general formula (Ia) generating a carboxy group by an acid and a partial structure represented by the general formula (Ib) generating a phenolic hydroxyl group by an acid , Will be described in more detail.

In the formulas (Ia) and (Ib), R ¹ represents an alkyl group or a cycloalkyl group. The alkyl group for R &lt; ¹ &gt; may be linear or branched.

The preferable number of carbon atoms of the alkyl group in R ¹ is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 7.

The preferable number of carbon atoms of the cycloalkyl group in R ¹ is preferably 3 to 20, more preferably 3 to 10, and still more preferably 5 to 7.

When these carbon atoms have a substituent, they include the carbon number of the substituent.

The alkyl group for R ¹ may be, for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group and n-decyl group.

Examples of the cycloalkyl group for R ¹ include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group and an isobornyl group.

The alkyl group and cycloalkyl group in R ¹ may have a substituent.

Examples of the substituent in the alkyl group and the cycloalkyl group include an alkyl group having 1 to 10 carbon atoms (such as a methyl group, an ethyl group, a propyl group or a butyl group), a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, A halogen atom, a chlorine atom, a bromine atom and an iodine atom), a cyano group, a nitro group, a hydroxyl group, and an alkoxy group having 1 to 10 carbon atoms. These substituents may be further substituted by the above substituents.

The alkyl group or cycloalkyl group in R ¹ is preferably an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or an aralkyl group having 7 to 11 carbon atoms, an alkyl group having 1 to 6 carbon atoms , A cycloalkyl group having 3 to 6 carbon atoms, or a benzyl group, more preferably an ethyl group or a cyclohexyl group, and particularly preferably an ethyl group.

In the general formulas (Ia) and (Ib), R ² represents an alkyl group. The alkyl group for R ² may be linear or branched.

The alkyl group in R ² preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 7 carbon atoms. When these carbon atoms have a substituent, they include the carbon number of the substituent.

As the alkyl group for R ² , a methyl group is particularly preferable.

In the general formula (Ib), Ar ¹ represents a divalent aromatic group, and the divalent aromatic group in Ar ¹ is not particularly limited and examples thereof include a phenylene group, a substituted phenylene group, a naphthylene group, a substituted naphthylene group and the like And is preferably a phenylene group or a substituted phenylene group, more preferably a phenylene group, still more preferably a 1,4-phenylene group.

The divalent aromatic group in Ar ¹ may have a substituent on the aromatic ring. Examples of the substituent include alkyl groups having 1 to 10 carbon atoms (such as a methyl group, an ethyl group, a propyl group and a butyl group), a cycloalkyl group having a carbon number of 3 to 10 A halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, nitro group, hydroxyl group, and alkoxy group having 1 to 10 carbon atoms. May be further substituted by the substituent.

The structural unit (a1) preferably contains at least one of the partial structures represented by the general formula (Ia) and the general formula (Ib) in which the carboxyl group or the phenolic hydroxyl group is protected.

As the carboxylic acid monomer capable of forming the structural unit (a1) containing the partial structure represented by the general formula (Ia) by protecting the carboxyl group, a carboxylic acid monomer which can be the structural unit (a1) by protecting the carboxyl group is used For example, monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, and? -Methyl-p-carboxystyrene; And dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid. As the structural unit (a1), a structural unit derived from a carboxylic acid in which these carboxyl groups are protected is preferable.

As the monomer having a phenolic hydroxyl group capable of forming the structural unit (a1) containing a partial structure represented by the general formula (Ib) by protecting the phenolic hydroxyl group, the structural unit (a1) For example, hydroxystyrenes such as p-hydroxystyrene,? -Methyl-p-hydroxystyrene, and the like, as described in paragraphs [0011] to [0016] of JP-A-2008-40183 , 4-hydroxybenzoic acid derivatives described in paragraphs [0007] to [0010] of Japanese Patent No. 2888454, addition reaction products of 4-hydroxybenzoic acid and glycidyl methacrylate, 4-hydroxybenzoic acid derivatives such as 4- An addition reaction product of a hydroxybenzoic acid and glycidyl acrylate, and the like.

Of these, α-methyl-p-hydroxystyrene, compounds described in paragraphs [0011] to [0016] of Japanese Patent Application Publication No. 2008-40183, compounds described in paragraphs [0007] to [0010] of Japanese Patent No. 2888454 A 4-hydroxybenzoic acid derivative, an addition reaction product of 4-hydroxybenzoic acid and glycidyl methacrylate, and an addition reaction product of 4-hydroxybenzoic acid and glycidyl acrylate are more preferable.

Particularly preferred as the structural unit (a1) is a structural unit represented by the following general formula (III).

In the general formula (III), R ⁵ represents an alkyl group or a cycloalkyl group, and preferred embodiments of R ⁵ are the same as those of R ¹ in formulas (Ia) and (Ib).

In the general formula (III), R ⁶ represents a hydrogen atom or a methyl group.

Specific preferred examples of the radical polymerizable monomer used for forming the structural unit represented by the general formula (III) include 1-ethoxyethyl methacrylate, 1-ethoxyethyl acrylate, 1-methoxy Ethyl methacrylate, ethyl methacrylate, 1-methoxyethyl acrylate, 1-n-butoxyethyl methacrylate, 1-n-butoxyethyl acrylate, 1-isobutoxyethyl methacrylate, , 1- (2-ethylhexyloxy) ethyl methacrylate, 1- (2-ethylhexyloxy) ethyl acrylate, 1-n-propoxyethyl methacrylate, , 1-cyclohexyloxyethyl methacrylate, 1-cyclohexyloxyethyl acrylate, 1- (2-cyclohexylethoxy) ethyl methacrylate, 1- (2-cyclohexylethoxy) Benzyloxyethyl methacrylate, 1-benzyloxyethyl acrylate, and the like. , Particularly preferable examples are a-ethoxyethyl acrylate-ethoxyethyl methacrylate and 1 to 1. These monomers may be used alone or in combination of two or more.

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

Here, R ⁵ and R ⁶ each have the same meaning as R ⁵ and R ⁶ in the general formula (III).

The structural unit (a1) is obtained by polymerizing a protected carboxyl group or a phenolic hydroxyl group-containing monomer with a structural unit (a2) to (a5) described below or a precursor thereof and then reacting the carboxyl group or the phenolic hydroxyl group with a vinyl ether compound Can also be formed. Specific examples of preferred structural units thus formed are the same as the structural units derived from the preferred specific examples of the radical polymerizable monomer.

As specific preferred examples of the structural unit (a1), the following structural units can be exemplified.

The content of the structural unit (a1) in the total structural units constituting the specific resin is preferably 10 to 80 mol%, more preferably 15 to 70 mol%, and particularly preferably 20 to 60 mol%. By containing the structural unit (a1) in the above ratio, a photosensitive resin composition having high sensitivity and a large exposure latitude can be obtained.

<< Structural unit (a2) >>

(A2) having at least one of a partial structure represented by the following formula (IIa) which forms a carboxy group by an acid and a partial structure partial unit represented by the following formula (IIb) which generates a phenolic hydroxyl group by an acid ) Will be described in more detail.

In the general formulas (IIa) and (IIb), R ³ represents a tertiary alkyl group, a 2-tetrahydropyranyl group or a 2-tetrahydrofuranyl group, R ⁴ represents a tertiary alkyl group, tert- A tetrahydropyranyl group, or a 2-tetrahydrofuranyl group, Ar ² represents a divalent aromatic group, and a broken line portion represents a bonding site with another structure.

The tertiary alkyl group for R ³ and R ⁴ preferably has 4 to 20 carbon atoms, more preferably 4 to 14 carbon atoms, and more preferably 4 to 8 carbon atoms.

A tertiary alkyl group in R ^3, 2-tetrahydropyranyl group, and a 2-tetrahydrofuranyl group, a tertiary alkyl group in the R ^4, tert- butoxycarbonyl group, 2-tetrahydropyranyl group, and a 2 -Tetrahydrofuranyl group and the bivalent aromatic group in Ar ² may have a substituent and examples of the substituent include an alkyl group having 1 to 10 carbon atoms (such as a methyl group, an ethyl group, a propyl group or a butyl group), a cycloalkyl group having a carbon number of 3 to 10 An aryl group having 6 to 10 carbon atoms, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, nitro group, hydroxyl group and alkoxy group having 1 to 10 carbon atoms. These substituents may be further substituted by the above substituents.

The tertiary alkyl group in R ³ and R ⁴ is more preferably at least one selected from the group consisting of the groups represented by the following general formula (V).

^{-C (R 9 R 10 R 11} ) (V)

In formula (V), R ⁹ , R ¹⁰ and R ¹¹ each independently represent an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms Or both of R ⁹ , R ¹⁰ and R ¹¹ may be bonded to each other to form a ring with the carbon atom to which they are bonded to form a ring.

The alkyl group having 1 to 12 carbon atoms represented by R ⁹ , R ¹⁰ and R ^{11 in} the general formula (V) may be linear or branched, and examples thereof include a methyl group, ethyl group, n-propyl group, butyl group, n-pentyl group, neopentyl group, n-hexyl group, texyl group (2,3-dimethyl-2- n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, and n-decyl group.

Examples of the cycloalkyl group having 3 to 12 carbon atoms for R ⁹ , R ¹⁰ and R ¹¹ include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, Isobornyl group and the like.

Examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a tolyl group, a xylyl group, a cumenyl group, and a 1-naphthyl group.

Examples of the aralkyl group having 7 to 12 carbon atoms include benzyl group,? -Methylbenzyl group, phenethyl group, naphthylmethyl group and the like.

Further, R ⁹ , R ¹⁰ and R ¹¹ may combine with each other to form a ring together with the carbon atom to which they are bonded. Examples of the ring structure when R ⁹ and R ¹⁰ , R ⁹ and R ¹¹ , or R ¹⁰ and R ¹¹ are bonded to each other include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, A furanyl group, an adamantyl group, and a tetrahydropyranyl group.

R ³ in the general formula (IIa) is preferably a tertiary alkyl group having 4 to 12 carbon atoms, a 2-tetrahydropyranyl group, or a 2-tetrahydrofuranyl group, more preferably a tertiary alkyl group having 4 to 8 carbon atoms More preferably a tertiary alkyl group, a 2-tetrahydropyranyl group or a 2-tetrahydrofuranyl group, more preferably a t-butyl group or a 2-tetrahydropyranyl group, or a 2-tetrahydrofuranyl group, A butyl group or a 2-tetrahydrofuranyl group is particularly preferred.

R ⁴ in the general formula (IIb) is preferably a tertiary alkyl group having 4 to 12 carbon atoms, a 2-tetrahydropyranyl group, a tert-butoxycarbonyl group or a 2-tetrahydrofuranyl group, More preferably a tertiary alkyl group of 4 to 12 carbon atoms, a 2-tetrahydropyranyl group, or a 2-tetrahydrofuranyl group, more preferably a t-butyl group, a 2-tetrahydropyranyl group, or a 2-tetrahydrofuranyl group More preferably a 2-tetrahydropyranyl group, or a 2-tetrahydrofuranyl group is particularly preferable.

In the general formula (IIb), Ar ² represents a divalent aromatic group and has -OCH (OR ¹ ) (R ² ) on the aromatic ring.

A preferred embodiment of Ar ^{2 in} the general formula (IIb) is the same as the preferred embodiment of Ar ¹ in the general formula (IIa).

The structural unit (a2) of the present invention contains a protected carboxy group represented by the formula (IIa) and / or a protected phenolic hydroxyl group represented by the formula (IIb).

The carboxylic acid monomer capable of forming the structural unit (a2) having the partial structure represented by the general formula (IIa) by protecting the carboxyl group can be used as long as it can be the structural unit (a2) by protecting the carboxyl group, Examples thereof include monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, and? -Methyl-p-carboxystyrene; And dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid. As the structural unit (a2), a structural unit derived from a carboxylic acid in which these carboxyl groups are protected is preferable.

As the monomer having a phenolic hydroxyl group capable of forming the structural unit (a2) having the partial structure represented by the general formula (IIb) by protecting the phenolic hydroxyl group, the structural unit (a2) is protected by protecting the phenolic hydroxyl group If it can be used, it can be used. For example, hydroxystyrenes such as p-hydroxystyrene and? -Methyl-p-hydroxystyrene, compounds described in paragraphs 0011 to 0016 of Japanese Patent Application Laid-Open No. 2008-40183, 4-hydroxybenzoic acid derivative as described in JP-A-0007-1010, an addition reaction product of 4-hydroxybenzoic acid and glycidyl methacrylate, an addition reaction product of 4-hydroxybenzoic acid and glycidyl acrylate, have.

Of these, α-methyl-p-hydroxystyrene, compounds described in paragraphs [0011] to [0016] of Japanese Patent Application Publication No. 2008-40183, compounds described in paragraphs [0007] to [0010] of Japanese Patent No. 2888454 A 4-hydroxybenzoic acid derivative, an addition reaction product of 4-hydroxybenzoic acid and glycidyl methacrylate, and an addition reaction product of 4-hydroxybenzoic acid and glycidyl acrylate are more preferable.

Particularly preferred as the structural unit (a2) is a structural unit represented by the following general formula (IV).

In the general formula (IV), R ⁷ represents a tertiary alkyl group, a 2-tetrahydropyranyl group or a 2-tetrahydrofuranyl group, and R ⁸ represents a hydrogen atom or a methyl group.

In the general formula (IV), preferred examples of R ⁷ are the same as those of R ^{3 in} the general formula (IIa).

Preferable specific examples of the radical polymerizable monomer used for forming the structural unit represented by the general formula (IV) include, for example, tert-butyl methacrylate, tert-butyl acrylate, tetrahydro- Methyl-2-adamantyl methacrylate, 2-methyl-2-adamantyl acrylate, 1-methylcyclohexyl methacrylate, 1-methylcyclohexyl methacrylate, 2-yl methacrylate, tetrahydro-2H-furan-2-yl acrylate, and the like. In particular, tert-butyl methacrylate, tert-butyl acrylate 2-yl methacrylate, tetrahydro-2H-furan-2-yl methacrylate, and tetrahydro-2H-furan-2-yl acrylate. The structural units derived from these radical polymerizable monomers may be used singly or in combination of two or more.

As specific preferred examples of the structural unit (a2), the following structural units can be exemplified.

The content of the structural unit (a2) in the total structural units constituting the specific resin is preferably 5 to 60 mol%, more preferably 10 to 50 mol%, and particularly preferably 10 to 40 mol%. By containing the structural unit (a2) in the above ratio, a photosensitive resin composition having high sensitivity and a large exposure latitude can be obtained.

&Lt; Cross-linking agent &

The specific resin contains a crosslinkable group.

The crosslinkable group may be either one which forms a covalent bond by reacting with the above-mentioned acid group, or a crosslinkable group which forms a covalent bond by the action of heat or light.

The structural unit (a3) having an epoxy group or an oxetanyl group is preferable as a covalent bond by reacting with an acid group, and the structural unit (a3) having a crosslinkable group to form a covalent bond by the action of heat or light includes a carbon- desirable. Among these crosslinkable groups, it is preferable to react with an acid group to form a covalent bond.

The crosslinkable group is preferably a structural unit (a3) having an epoxy group or an oxetanyl group (hereinafter appropriately referred to as "structural unit (a3)") contained in a specific resin.

As the structural unit (a3), both groups of an epoxy group and an oxetanyl group may be contained.

The structural unit (a3) having an epoxy group or an oxetanyl group is preferably a structural unit having an alicyclic epoxy group or an oxetanyl group, more preferably a structural unit having an oxetanyl group.

The alicyclic epoxy group is a group in which an aliphatic ring and an epoxy ring form a condensed ring. Specific examples thereof include 3,4-epoxycyclohexyl group, 2,3-epoxycyclohexyl group, 2,3-epoxycyclopene T-butyl group and the like.

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 having an epoxy group or an oxetanyl group may contain at least one epoxy group or oxetanyl group in one structural unit, may contain at least one epoxy group and at least one oxetanyl group, may contain two or more epoxy groups, An oxetanyl group, an epoxy group, an oxetanyl group, and an oxetanyl group. The epoxy group and oxetanyl group are preferably one to three in total, more preferably one or both of an epoxy group and an oxetanyl group, It is more preferable to have one.

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 Epoxycyclohexyl methacrylate, glycidyl acrylate, glycidyl? -N-butyl acrylate,? -Epoxybutyl acrylate,? -Epoxybutyl methacrylate, Epoxy heptyl,? -Ethylacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and Japanese Patent No. 4168443 Compounds containing an alicyclic epoxy skeleton described in [0031] to [0035], and the like.

Examples of the radically polymerizable monomer used for forming the oxetanyl group-containing structural unit include (meth) acrylates having an oxetanyl group as described in paragraphs [0011] to [0016] of JP 2001-330953 A, Acrylic acid esters and the like.

Examples of the radical polymerizable monomer used for forming the structural unit having an epoxy group or an oxetanyl group are monomers containing a methacrylate ester structure and monomers containing an acrylic ester structure.

Among these radically polymerizable monomers, preferred are compounds containing an alicyclic epoxy skeleton described in paragraphs [0034] to [0035] of Japanese Patent No. 4168443, and compounds containing an alicyclic epoxy skeleton as disclosed in Japanese Patent Laid-Open No. 2001-330953 (Meth) acrylic acid ester having an oxetanyl group as described in paragraphs [0011] to [0016] of Japanese Patent Application Laid-Open No. 2001-330953, to be. Among these, preferred are acrylic esters such as 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, methyl (3-ethyloxetan-3-yl) (3-ethyloxetan-3-yl) methyl, and methacrylic acid (3-ethyloxetan-3-yl) methyl. These structural units may be used singly or in combination of two or more.

As specific preferred examples of the structural unit (a3), the following structural units can be exemplified.

The content of the structural unit (a3) having an epoxy group or an oxetanyl group in the whole structural units constituting the specific resin is preferably from 10 to 80 mol%, more preferably from 15 to 70 mol%, still more preferably from 20 to 65 mol% Is particularly preferable. By containing the structural unit having an epoxy group or an oxetanyl group in the above ratio, the physical properties of the cured film formed by the photosensitive resin composition become good.

[Acids]

The specific resin contains an acid group within a range that does not make the specific resin alkali-soluble.

The acid group contained in the specific resin is preferably a structural unit (a4) having at least one acid group selected from a carboxyl group, a carboxylic acid anhydride residue and a phenolic hydroxyl group (hereinafter referred to as "structural unit (a4) . The structural unit (a4) is more preferably a structural unit having a carboxyl group and / or a phenolic hydroxyl group.

Examples of the radically polymerizable monomer used for forming the structural unit having a carboxyl group include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; And unsaturated carboxylic acids such as dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid.

As the radical polymerizable monomer used for forming the structural unit having a carboxylic acid anhydride residue, for example, maleic anhydride, itaconic anhydride and the like are preferably used.

Examples of the radically polymerizable monomer used for forming the structural unit having a phenolic hydroxyl group include hydroxystyrenes such as p-hydroxystyrene and? -Methyl-p-hydroxystyrene, Compounds described in paragraphs [0011] to [0016] of the publication, 4-hydroxybenzoic acid derivatives described in paragraphs [0007] to [0010] of Japanese Patent No. 2888454, 4-hydroxybenzoic acid derivatives and 4-hydroxybenzoic acid derivatives such as glycidyl methacrylate An addition reaction product of 4-hydroxybenzoic acid and glycidyl acrylate, and the like.

Among them, methacrylic acid, acrylic acid, the compounds described in paragraphs [0011] to [0016] of Japanese Patent Application Laid-Open No. 2008-40183 and the compounds described in paragraphs [0007] to [0010] of Japanese Patent No. 2888454 Benzoic acid derivatives, addition reaction products of 4-hydroxybenzoic acid and glycidyl methacrylate, and addition reaction products of 4-hydroxybenzoic acid and glycidyl acrylate are more preferable, The compounds of 4-hydroxybenzoic acid derivatives described in paragraphs [0007] to [0010] of Japanese Patent No. 2888454, the addition of 4-hydroxybenzoic acid and glycidyl methacrylate Particularly preferred is a reactant, an addition reaction product of 4-hydroxybenzoic acid and glycidyl acrylate. These structural units may be used singly or in combination of two or more.

As specific preferred examples of the structural unit (a4), the following structural units can be exemplified.

The content of the structural unit (a4) having at least one group selected from a carboxyl group, a carboxylic acid anhydride residue and a phenolic hydroxyl group in the whole structural units constituting the specific resin is preferably from 2 to 35 mol%, more preferably from 5 to 20 mol% , Still more preferably from 8 to 12 mol%. When the specific resin contains the structural unit (a4) in the above ratio, a high sensitivity can be obtained and the developability can be improved.

&Lt; Other Structural Unit (a5) >

The specific resin may contain another structural unit (a5) (hereinafter, appropriately referred to as &quot; structural unit (a5) &quot;) within the range not hindering the effect of the present invention.

Examples of the radical polymerizable monomer used for forming the structural unit (a5) include the compounds described in paragraphs [0021] to [0024] of JP 2004-264623 A (however, Excluding units (a1) to (a4)).

Preferable examples of the structural unit (a5) include a structural unit derived from at least one member selected from the group consisting of a hydroxyl group-containing unsaturated carboxylic acid ester, an alicyclic structure-containing unsaturated carboxylic acid ester, styrene, and N-substituted maleimide.

Among these, from the viewpoint of improvement of electrical properties, (meth) acrylic acid tricyclo [5.2.1.0 ^2,6 ] decan-8-yl, (meth) acrylic acid tricyclo [5.2.1.0 ^2,6 ] decan- , (Meth) acrylic acid esters containing an alicyclic structure such as isobornyl (meth) acrylate, cyclohexyl (meth) acrylate and 2-methylcyclohexyl (meth) acrylate, or hydrophobic monomers such as styrene are preferable. From the viewpoint of sensitivity, 2-hydroxyethyl (meth) acrylate and N-substituted maleimide are preferable. Among them, (meth) acrylic acid esters containing an alicyclic structure are more preferable.

These (a5) components may be used singly or in combination of two or more.

The content of the structural unit (a5) in the case of containing the structural unit (a5) among the whole structural units constituting the specific resin is preferably from 1 to 50 mol%, more preferably from 5 to 40 mol% And particularly preferably from 5 to 30 mol%.

Specific examples of the combination of the structural units constituting the specific resin include a structural unit derived from a radically polymerizable compound containing an acid group protected with an acid decomposable group, a structural unit derived from an unsaturated carboxylic acid, and an epoxy group or an oxetanyl group And a structural unit derived from a radically polymerizable compound.

The weight-average molecular weight of the specific resin in the present invention is preferably 1,000 to 100,000, more preferably 2,000 to 50,000, and still more preferably 5,000 to 15,000. The weight average molecular weight in the present invention is preferably a polystyrene reduced weight average molecular weight determined by gel permeation chromatography (GPC).

Various methods are known for the synthesis of a specific resin. For example, a method of producing a resin containing a radically polymerizable monomer used for forming at least the structural unit (a1), the structural unit (a2), and the structural unit (a3) The radical polymerizable monomer mixture can be synthesized by polymerization in an organic solvent using a radical polymerization initiator.

The specific resin is a copolymer obtained by adding a vinyl ether compound or vinyl thioether compound to an acid anhydride group in a precursor copolymer obtained by copolymerizing an unsaturated polycarboxylic acid anhydride at a temperature of about room temperature to about 100 ° C in the absence of an acid catalyst Coalescence is also desirable.

Examples of such a specific resin include a copolymer obtained by adding 1 mole of ethyl vinyl ether to the acid anhydride group in glycidyl (meth) acrylate / maleic anhydride / N-cyclohexylmaleimide / styrene copolymer, ) Glycidyl acrylate / maleic anhydride / N-cyclohexylmaleimide / styrene copolymer with isobutyl vinyl ether in an amount of 1 part by mole based on the acid anhydride group.

Hereinafter, preferred specific resins used in the present invention are exemplified as specific resins A to U, but the present invention is not limited thereto. In addition, the weight average molecular weight of each specific resin shown below is in the range of 5,000 to 15,000.

Specific resin A: a copolymer of MAA / MAEVE / OXE-30 / HEMA (molar ratio: 10/40/30/20, I / O value: 0.660, acid value: 36.63 mgKOH / g)

Specific resin B: Copolymer of MAA / MAEVE / OXE-30 / HEMA (molar ratio: 6/40/34/20, I / O value: 0.623, acid value: 21.43 mgKOH / g)

Specific resin C: Copolymer of MAA / MAEVE / OXE-30 / HEMA (molar ratio: 19/40/30/11, I / O value: 0.670, acid value: 71.45 mgKOH / g)

Specific resin D: a copolymer of MAA / MAEVE / OXE-30 / HEMA (molar ratio: 3/40/30/27, I / O value: 0.653, acid value: 10.77 mgKOH / g)

Specific resin E: Copolymer of MAA / MAEVE / OXE-30 / HEMA (molar ratio: 22/40/30/8, I / O value: 0.673, acid value: 83.47 mg KOH / g)

Specific resin F: copolymer of MAA / MAEVE / OXE-30 / HEMA (molar ratio: 27/40/30/3, I / O value: 0.679, acid value: 103.98 mgKOH / g)

A copolymer of a specific resin G: MAA / MAEVE / OXE-30 / HEMA (molar ratio: 9/33/21/37, I / O value: 0.792, acid value: 34.40 mgKOH / g)

A copolymer of a specific resin H: MAA / MAEVE / OXE-30 / HEMA / St / CMI (molar ratio: 10/30/20/20/10/10, I / O value: 0.657, acid value: 38.10 mgKOH / g)

A copolymer of a specific resin I: MAA / StOEVE / OXE-30 / HEMA (molar ratio: 10/35/30/25, I / O value: 0.625, acid value: 35.54 mgKOH / g)

Specific resin J: MAA / MAEVE / OXE-30 / MMA / DCPM (molar ratio: 17/18/10/18/5, I / O value: 0.612, acid value: 67.56 mgKOH / g)

Specific resin K: copolymer of MAA / MAEVE / OXE-30 / MMA (molar ratio: 17/33/25/25, I / O value: 0.615, acid value: 69.16 mgKOH / g)

Specific resin L: Copolymer of MAA / MAEVE / GMA / HEMA (molar ratio: 10/40/4/10, I / O value: 0.693, acid value: 39.58 mgKOH / g)

(Mass ratio) of a copolymer of a specific resin M: MAA / MAEVE / HEMA (molar ratio: 25/50/25) to a copolymer of MAEVE / HEMA / GMA (molar ratio: 33.3 / 16.7 / / O value: 0.757, acid value: 39.92 mgKOH / g)

(Mass ratio) of a copolymer of a specific resin N: MAA / MAEVE / HEMA (molar ratio: 25/50/25) to a copolymer of MAEVE / HEMA / OXE-30 (molar ratio: 33.3 / 16.7 / 50) (I / O value: 0.660, acid value: 36.63 mgKOH / g)

(Molar ratio: 20/25/30/25, I / O value: 0.792, acid value: 78.33 mgKOH / g) of a specific resin O: MAA / HEMA / MAEVE / OXE-

Copolymer of specific resin P: MAA / HEMA / MAEVE / OXE-30 (molar ratio: 22/23/30/25, I / O value: 0.795, acid value: 86.70 mgKOH / g)

Specific resin Q: Copolymer of MAA / MAEVE / OXE-30 (molar ratio: 23/40/37, I / O value: 0.614, acid value: 85.33 mgKOH / g)

Copolymer of specific resin R: MAA / MAEVE / OXE-30 (molar ratio: 29/10/61, I / O value: 0.622, acid value: 106.24 mg KOH / g)

A copolymer of a specific resin S: MAA / HEMA / MAEVE / OXE-30 (molar ratio: 27/18/25/30, I / O value: 0.791, acid value: 107.08 mgKOH / g)

Specific resin T: MAA / MATHF / OXE-30 / HEMA copolymer (molar ratio: 10/40/30/20, I / O value: 0.686, acid value: 36.82 mgKOH / g)

A copolymer of specific resin U: MAA / MATHF / OXE-30 / HEMA (molar ratio: 10/40/25/25, I / O value: 0.730, acid value: 37.49 mgKOH / g)

Examples of the synthesis of the above specific resins will be described later. The abbreviations of the monomers constituting each specific resin are as follows.

MAA: methacrylic acid

MAEVE: 1-ethoxyethyl methacrylate

OXE-30: 3-ethyl-3-oxetanylmethyl methacrylate

HEMA: Hydroxyethyl methacrylate

EtMA: Ethyl methacrylate

HMA: hexyl methacrylate

GMA: glycidyl methacrylate

St: Styrene

CMI: N-cyclohexylmaleimide

StOEVE: 4- (1-ethoxyethyloxy) styrene

DCPM: dicyclopentanyl methacrylate

MMA: methyl methacrylate

MATHF: 2-Tetrahydrofuranyl methacrylate

The content of the specific resin in the photosensitive resin composition of the present invention is preferably 20 to 99% by mass, more preferably 40 to 97% by mass, and more preferably 60 to 95% by mass based on the total solid content of the photosensitive resin composition More preferable. When the content is within this range, pattern formation property upon development becomes good. The solid content of the photosensitive resin composition means an amount obtained by removing volatile components such as a solvent.

In the photosensitive resin composition of the present invention, resins other than the specific resin may be used in combination as long as the effect of the present invention is not hindered. However, the content of the resin other than the specific resin is preferably smaller than the content of the specific resin from the viewpoint of developability.

(The radiation-sensitive acid generator (B))

The photosensitive resin composition of the present invention contains a radiation-sensitive acid generator (acid generator).

As the acid generator used in the present invention, a compound which generates an acid upon exposure to an actinic ray having a wavelength of 300 nm or longer, preferably 300-450 nm is preferable, but the chemical structure is not limited thereto. Also, with respect to an acid generator which does not directly react with an actinic ray having a wavelength of 300 nm or more, a compound capable of generating an acid upon exposure to an actinic ray having a wavelength of 300 nm or more by being used in combination with a sensitizer described below can be preferably used in combination with a sensitizer have.

As the acid generator used in the present invention, an acid generator that generates an acid with a pKa of 4 or less is preferable, and an acid generator that generates an acid with a pKa of 3 or less is more preferable.

Examples of the acid generator include trichloromethyl-s-triazine, sulfonium salts and iodonium salts, quaternary ammonium salts, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds have. Of these, oxime sulfonate compounds are preferably used from the viewpoint of high sensitivity.

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

Specific examples of these acid generators include the following.

As trichloromethyl-s-triazines, 2- (3-chlorophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -S-triazine, 2- (4-methylthiophenyl) -bis (4,6-trichloromethyl) Triazine, 2-piperonyl-bis (4,6-trichloromethyl) -s-triazine, 2- [2- (furan- (4,6-trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-2-yl) ethenyl] -bis (4,6-trichloromethyl) -s-triazine, or 2- (4-methylphenyl) ethenyl] -bis Naphthyl) -bis (4,6-trichloromethyl) -s-triazine and the like.

As the diaryl iodonium salts, diphenyl iodonium trifluoroacetate, diphenyl iodonium trifluoromethane sulfonate, 4-methoxyphenylphenyl iodonium trifluoromethane sulfonate, 4-methoxy (2'-hydroxy-1'-tetradecarboxy) phenyl iodonium trifluoromethanesulfonate, phenyl 4- (2'-hydroxy-1'- -Tetradecaoxy) phenyl iodonium hexafluoroantimonate, or phenyl-4- (2'-hydroxy-1'-tetradecaoxy) phenyl iodonium p-toluenesulfonate.

As the triarylsulfonium salts, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyldiphenyl Sulfonium trifluoroacetate, 4-phenylthiophenyldiphenylsulfonium trifluoromethane sulfonate, 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 imide sulfonate derivative, trifluoromethylsulfonyloxybicyclo [2.2.1] -hept-5-ene-dicarboxyimide, succinimide trifluoromethylsulfonate, phthalimide trifluoromethylsulfone N-hydroxynaphthalimide methanesulfonate, N-hydroxy-5-norbornene-2,3-dicarboxyimidopropane sulfonate, and the like.

The photosensitive resin composition of the present invention preferably contains an oxime sulfonate compound having at least one oxime sulfonate group represented by the following structure (1) as the acid generator (B).

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

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

In the general 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, may represent an alkoxy group or a cyano group of 1 to 4, the R ^1A, a phenyl group, when a biphenyl group, a naphthyl group or anthranyl group, these groups, an alkyl group of a halogen atom, a hydroxyl group, the number of 1 to 4 carbon atoms, carbon atoms, An alkoxy group having 1 to 4 carbon atoms, and a nitro group. 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, A phenyl group, a naphthyl group which may be substituted with W, or an anthranyl group, a dialkylamino group, a morpholino group, or a 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 6-membered ring may be bonded to a benzene ring which may have 1 or 2 arbitrary substituents. 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 Lt; / RTI &gt;

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, Butyl group, n-pentyl group, isoamyl group, n-hexyl group, or 2-ethylbutyl group.

The halogenated alkyl group having 1 to 4 carbon atoms represented by R ^1A includes, for example, a chloromethyl group, a trichloromethyl group, a trifluoromethyl group, or 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 chlorine atom, a bromine atom, an iodine atom, etc.), a hydroxyl group, an alkyl group having 1 to 4 carbon atoms (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- 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- , n-amyl group, i-amyl group, s-amyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group and n-decyl group.

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, N-decyloxy group, 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, n-amyl group and the like.

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 o-tolyl, m-tolyl, p-tolyl, o-ethylphenyl, m- (Propyl) phenyl group, p- (i-propyl) phenyl group, p- p-phenylphenyl group, o-methoxyphenyl group, m-methoxyphenyl group, p-methoxyphenyl group, o-ethoxyphenyl group, (n-butoxy) phenyl group, p- (i-butoxy) phenyl group, p- (P-amyloxy) phenyl group, p- (t-butoxy) phenyl group, p- ) Phenyl, p-chlorophenyl, p-bromophenyl, p-fluorophenyl, 2,4-dichlorophenyl, 2,4-dibromophenyl, 2,4-difluorophenyl, 2,4,6 - a dichlorophenyl group, a 2,4,6-tribromophenyl group, a 2,4 , A 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, Methyl-1-naphthyl group, 1-methyl-2-naphthyl group, 3-methyl-2-naphthyl group, 4- 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, Anthranyl group, a 10-methyl-1-anthranyl group, a 1- methyl-1-anthranyl group, Anthranyl group, 6-methyl-2-anthranyl group, 7-methyl-2-anthranyl group, 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, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i- , n-amyl group, i-amyl group, s-amyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group and n-decyl group.

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, N-decyloxy group, 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, n-amyl group and the like.

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, (Propyl) phenyl group, p- (i-propyl) phenyl group, p- p-phenylphenyl group, o-methoxyphenyl group, m-methoxyphenyl group, p-methoxyphenyl group, o-ethoxyphenyl group, (n-butoxy) phenyl group, p- (i-butoxy) phenyl group, p- (P-amyloxy) phenyl group, p- (t-butoxy) phenyl group, p- ) Phenyl, p-chlorophenyl, p-bromophenyl, p-fluorophenyl, 2,4-dichlorophenyl, 2,4-dibromophenyl, 2,4-difluorophenyl, 2,4,6 - a dichlorophenyl group, a 2,4,6-tribromophenyl group, a 2,4 , A 6-trifluorophenyl group, a pentachlorophenyl group, a pentabromophenyl group, a pentafluorophenyl group, and a p-biphenyl group.

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

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 having 1 to 5 carbon atoms represented by W include R ^2A or Specific examples of the alkyl group having 1 to 10 carbon atoms represented by R ^3A , 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 And the like.

R ^2A and R ^1A may combine with each other to form a 5-membered or 6-membered ring.

When R ^2A and R ^1A are bonded to each other to form a 5-membered or 6-membered ring, examples of the 5-membered or 6-membered ring include a carbocyclic group and a heterocyclic group, and examples thereof include cyclopentane, cyclohexane, Pyridine, pyrazine, morpholine, piperidine or piperazin ring may be used as the substituent. 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 systems. . 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 favorable aspects of the compound represented by the general formula (2) is a compound represented by the following general formula (2-1). The compound represented by the general formula (2-1) is a compound in which R ^2A and R ^1A in the general formula (2) are bonded to form a 5-membered ring.

In the general formula (2-1), R ^3A is, and R ^3A and agreement in the formula (2), X is an alkyl group, an alkoxy group, or a halogen atom, t is an integer of 0 to 3 And when t is 2 or 3, plural Xs may be the same or different.

The alkyl group represented by X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms.

The alkoxy group represented by X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms.

The halogen atom represented by X is preferably a chlorine atom or a fluorine atom.

As t, 0 or 1 is preferable.

In the general formula (2-1), t is 1, X is a methyl group, X is a substituted position in the ortho position, R ^3A is a straight-chain alkyl group having 1 to 10 carbon atoms, 7,7- Oxonoboronylmethyl group, or p-toluyl group is particularly preferable.

Specific examples of the oxime sulfonate compound represented by the general formula (2-1) include the following compounds (i), (ii), (iii) and (iv) It may be used singly or in combination of two or more. The compounds (i) to (iv) are commercially available.

It may also be used in combination with other kinds of specific acid generators.

As one of preferred embodiments of the acid generator represented by the general 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 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, W represents a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, An alkoxy group, 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 general formula (2) is preferably a compound represented by the following general 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, a cyano group or a nitro group, Represents an integer. 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 represents a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, An alkoxy group, 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 general formula (2-2) include a methyl group, ethyl group, n-propyl group, n-butyl group, n-octyl group, trifluoromethyl group, pentafluoroethyl group, Propyl group, an n-butyl group or a p-tolyl group is particularly preferable, and a perfluoro-n-butyl group, a p-tolyl group, a 4-chlorophenyl group or a pentafluorophenyl group is preferable and a methyl group, Do.

As the halogen atom represented by R ^4A , a fluorine atom, a chlorine atom or a bromine atom is preferable.

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.

Among the acid generators represented by the general formula (2), preferable examples of the compound included in the acid generator represented by the general formula (2-2) include those in which R ^1A is a phenyl group or 4- R ^2A is a cyano group, and R ^3A is a methyl group, an ethyl group, a n-propyl group, an n-butyl group or a 4-tolyl group.

Among the acid generators represented by the general formula (2), particularly preferred examples of the compounds included in the acid generators represented by the general formula (2-2) are shown below, but the present invention is not limited thereto.

? - (methylsulfonyloxyimino) benzyl cyanide (R ^1A = phenyl group, R ^2A = -CN group, R ^3A = methyl group)

? - (ethylsulfonyloxyimino) benzyl cyanide (R ^1A = phenyl group, R ^2A = -CN group, R ^3A = ethyl group)

(R ^1A = phenyl group, R ^2A = -CN group, R ^3A = n-propyl group)

(R ^1A = phenyl group, R ^2A = -CN group, R ^3A = n-butyl group)

benzyl cyanide (R ^1A = phenyl group, R ^2A = -CN group, R ^3A = 4-tolyl group)

methoxyphenyl] acetonitrile (R ^1A = 4-methoxyphenyl group, R ^2A = -CN group, R ^3A = methyl group)

methoxyphenyl) acetonitrile (R ^1A = 4-methoxyphenyl group, R ^2A = -CN group, R ^3A = ethyl group)

methoxyphenyl) acetonitrile (R ^1A = 4-methoxyphenyl group, R ^2A = -CN group, R ^3A = n-propyl group)

(R ^1A = 4-methoxyphenyl group, R ^2A = -CN group, R ^3A = n-butyl group)

methoxyphenyl) acetonitrile (R ^1A = 4-methoxyphenyl group, R ^2A = -CN group, R ^3A = 4-tolyl group)

Other favorable examples of the oxime sulfonate compound having at least one oxime sulfonate group represented by the above structure (1) are represented by the following general formulas (OS-3), (OS-4) -5). &Lt; / RTI &gt; Among these compounds, a compound represented by the general formula (OS-3) is more preferable.

In the general formulas (OS-3) to (OS-5), R ¹ represents an alkyl group, an aryl group or a heteroaryl group, and a plurality of R ^{2 s} present therein are each independently a hydrogen atom, an alkyl group, , Or a halogen atom, and a plurality of R ⁶ which may be present may independently represent 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 general formulas (OS-3) to (OS-5), the alkyl group, aryl group or heteroaryl group represented by R ¹ may have a substituent.

In the general formulas (OS-3) to (OS-5), the alkyl group represented by R ¹ is preferably an alkyl group having 1 to 30 carbon atoms in total which may have a substituent.

Examples of the substituent which the alkyl group represented by R ¹ may have include a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, and an aminocarbonyl group.

Examples of the alkyl group represented by R ¹ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an s-butyl group, An n-decyl group, a n-dodecyl group, a trifluoromethyl group, a perfluoropropyl group, a perfluorohexyl group, and a benzyl group.

In the general formulas (OS-3) to (OS-5), the aryl group represented by R ¹ is preferably an aryl group having a total of 6 to 30 carbon atoms and may have a substituent.

Examples of the substituent which the aryl group represented by R ¹ may have include halogen atoms, alkyl groups, alkyloxy groups, aryloxy groups, alkylthio groups, arylthio groups, alkyloxycarbonyl groups, aryloxycarbonyl groups, aminocarbonyl groups, An alkoxy group, an alkoxy group, an alkoxy group, an alkoxy group,

Examples of the aryl group represented by R ¹ include a phenyl group, p-methylphenyl group, p-chlorophenyl group, pentachlorophenyl group, pentafluorophenyl group, o-methoxyphenyl group and p-phenoxyphenyl group.

Of the general formulas (OS-3) to (OS-5), the heteroaryl group represented by R ¹ is preferably a heteroaryl group having 4 to 30 carbon atoms in total which may have a substituent.

Examples of the substituent which the heteroaryl group represented by R ¹ may have include a halogen atom, an alkyl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an aminocarbonyl group, A sulfonyl group, and an alkoxysulfonyl group.

In the general formulas (OS-3) to (OS-5), the heteroaryl group represented by R ¹ may be any as long as it contains at least one heteroaromatic ring. For example, the heteroaromatic ring and the benzene ring may be coordinated.

Examples of the heteroaryl group represented by R ¹ include a thiophene ring, a pyrrole ring, a thiazole ring, an imidazole ring, a furan ring, a benzothiophene ring, a benzothiazole ring, and a benzoimidazole ring which may have a substituent And a group obtained by subtracting one hydrogen atom from the ring selected in the group.

In the general formulas (OS-3) to (OS-5), R ² is preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or an alkyl group.

Of the general formulas (OS-3) to (OS-5), one or two of R ² present in two or more of the compounds are preferably an alkyl group, an aryl group or a halogen atom, and one of them is an alkyl group, And it is particularly preferable that one is an alkyl group and the remainder is a hydrogen atom.

In the general formulas (OS-3) to (OS-5), the alkyl group or aryl group represented by R ² may have a substituent.

Examples of the substituent which the alkyl group or aryl group represented by R ² may have include the same group as the substituent which the alkyl group or aryl group represented by R ¹ may have.

The alkyl group represented by R ² is preferably an alkyl group having 1 to 12 carbon atoms in total which may have a substituent and more preferably an alkyl group having 1 to 6 carbon atoms in total which may have a substituent.

Examples of the alkyl group represented by R ² include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, Propyl group, n-butyl group, i-butyl group, s-butyl group, or n-hexyl group is preferably a methyl group, More preferably a methyl group, an ethyl group, an n-propyl group, an n-butyl group or an n-hexyl group, and a methyl group is particularly preferable.

The aryl group represented by R ² is preferably an aryl group having a total of 6 to 30 carbon atoms which may have a substituent.

Examples of the aryl group represented by R ² include a phenyl group, a p-methylphenyl group, an o-chlorophenyl group, a p-chlorophenyl group, an o-methoxyphenyl group and a p-phenoxyphenyl group.

Examples of the halogen atom represented by R ² include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Among them, a chlorine atom or a bromine atom is preferable.

Among the general formulas (OS-3) to (OS-5), X represents O or S, and is preferably O.

In the general formulas (OS-3) to (OS-5), the ring containing X as a reduction is a 5-membered ring or a 6-membered ring.

In the general formulas (OS-3) to (OS-5), n represents 1 or 2, and when X is O, n is preferably 1. When X is S, n is 2 desirable.

In the general formulas (OS-3) to (OS-5), the alkyl group and alkyloxy group represented by R ⁶ may have a substituent.

In the general formulas (OS-3) to (OS-5), the alkyl group represented by R ⁶ is preferably an alkyl group having 1 to 30 carbon atoms in total which may have a substituent.

Examples of the substituent which the alkyl group represented by R ⁶ may have include a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, and an aminocarbonyl group.

Examples of the alkyl group represented by R ⁶ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an s- An n-decyl group, a n-dodecyl group, a trifluoromethyl group, a perfluoropropyl group, a perfluorohexyl group, and a benzyl group.

In the general formulas (OS-3) to (OS-5), the alkyloxy group represented by R ⁶ is preferably an alkyloxy group having 1 to 30 total carbon atoms which may have a substituent.

Examples of the substituent which the alkyloxy group represented by R ⁶ may have include a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, and an aminocarbonyl group.

Examples of the alkyloxy group represented by R ⁶ include a methyloxy group, an ethyloxy group, a butyloxy group, a hexyloxy group, a phenoxyethyloxy group, a trichloromethyloxy group, and an ethoxyethyloxy group.

Examples of the aminosulfonyl group represented by R ⁶ in formulas (OS-3) to (OS-5) include a methylaminosulfonyl group, a dimethylaminosulfonyl group, a phenylaminosulfonyl group, a methylphenylaminosulfonyl group, .

Examples of the alkoxysulfonyl group represented by R ⁶ in formulas (OS-3) to (OS-5) include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, .

Among the general formulas (OS-3) to (OS-5), m represents an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, Do.

The compound represented by the general formula (OS-3) is particularly preferably a compound represented by the following general formula (OS-6), (OS-10) or (OS-11) OS-4) is particularly preferably a compound represented by the following general formula (OS-7), and the compound represented by the general formula (OS-5) Or (OS-9).

In the formulas (OS-6) to (OS-11), R ¹ represents an alkyl group, an aryl group or a heteroaryl group, R ⁷ represents a hydrogen atom or a bromine atom, R ⁸ represents a hydrogen atom, R ⁹ represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, R ¹⁰ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or a chlorophenyl group, A hydrogen atom or a methyl group.

R ¹ in the formula (OS-6) ~ (OS -11) is the general formula (OS-3) ~ and R ¹ and agree in (OS-5), as a preferred aspect.

R ⁷ in the formula (OS-6) represents a hydrogen atom or a bromine atom, and is preferably a hydrogen atom.

R ⁸ in formulas (OS-6) to (OS-11) represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, Or a chlorophenyl group, and is preferably an alkyl group having 1 to 8 carbon atoms, a halogen atom, or a phenyl group, more preferably an alkyl group having 1 to 8 carbon atoms, further preferably an alkyl group having 1 to 6 carbon atoms, Particularly preferred.

R ⁹ in formulas (OS-8) and (OS-9) represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and is preferably a hydrogen atom.

R ¹⁰ in formulas (OS-8) to (OS-11) represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom.

In the oxime sulfonate compound, any of the three-dimensional structures (E, Z) of oxime may be a mixture or a mixture thereof.

Specific examples of the oxime sulfonate compounds represented by the above general formulas (OS-3) to (OS-5) include the following exemplified compounds, but the present invention is not limited thereto.

Another favorable embodiment of the oxime sulfonate compound having at least one oxime sulfonate group represented by the above structure (1) includes a compound represented by the following general formula (OS-1).

In formula (OS-1), R ¹ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, Lt; / RTI &gt; R ² represents an alkyl group or an aryl group.

In the general formula (OS-1), X is, -O-, -S-, -NH-, -NR 5 -, -CH 2 -, -CR 6 H-, or, -CR ⁶ R ⁷ - represents a , And R ⁵ to R ⁷ each independently represent an alkyl group or an aryl group.

In the formula (OS-1), R ²¹ to R ²⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, , A cyano group, or an aryl group. Two of R ²¹ to R ²⁴ may be bonded to each other to form a ring.

As R ²¹ to R ²⁴ , a hydrogen atom, a halogen atom, and an alkyl group are preferable, and an embodiment in which two R ²¹ to R ²⁴ groups are bonded together to form an aryl group is also preferable . Among them, the case where all of R ²¹ to R ²⁴ are hydrogen atoms is preferable from the viewpoint of sensitivity.

Each of the functional groups described above may further have a substituent.

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

In the general formula ^{(OS-2), R 1} , R 2, R 21 ~R 24 are, each ^{independently, R 1, R 2, R} 21 ~R 24 and agreement in the general formula (OS-1) (Synonymous), and preferred examples are also the same.

Of these, formula (OS-1) and the R ¹ in the formula (OS-2) a cyano group, or an aryl group, and the sun is more preferred, and represented by the general formula (OS-2), R ¹ A cyano group, a phenyl group or a naphthyl group is most preferable.

In the oxime sulfonate compound, the stereostructure (E, Z, etc.) of oxime or benzothiazole ring may be either or both of them.

Specific examples (Exemplary Compounds b-1 to b-34) of a compound represented by the general formula (OS-1) which can be used in the present invention are shown below, but the present invention is not limited thereto. In the specific examples, Me represents a methyl group, Et represents an ethyl group, Bn represents a benzyl group, and Ph represents a phenyl group.

Of these compounds, b-9, b-16, b-31 and b-33 are preferred from the viewpoint of compatibility between sensitivity and stability.

The photosensitive resin composition of the present invention preferably contains no 1,2-quinonediazide compound as an acid generator sensitive to an actinic ray. The reason for this is that the 1,2-quinonediazide compound generates a carboxyl group by a sequential photochemical reaction, but its quantum yield is 1 or less, and the sensitivity is lower than that of the oxime sulfonate compound.

On the other hand, the oxime sulfonate compound acts as a catalyst against deprotection of an acid-protected acid generated by the action of an actinic ray, so that an acid generated by the action of one photon contributes to a number of deprotection reactions, The quantum yield is greater than 1, for example, a large value such as several powers of 10, and it is presumed that high sensitivity is obtained as a result of so-called chemical amplification.

In the photosensitive resin composition of the present invention, the acid 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 specific resin.

The photosensitive resin composition of the present invention is preferably an acid generator which is sensitive to an actinic ray and does not contain a 1,2-quinonediazide compound. The reason is that the 1,2-quinonediazide compound generates a carboxy group by a sequential photochemical reaction, but its quantum yield is necessarily not more than 1, and compared with the oxime sulfonate compound used in the present invention , And the sensitivity is low. On the other hand, acid generators such as the oxime sulfonate compound of the present invention act as a catalyst for the deprotection of a protected acidic group in response to an actinic ray, It is presumed that one acid contributes to a number of deprotection reactions, and the quantum yield is more than 1, for example, a large value such as several powers of 10, and high sensitivity is obtained as a result of so-called chemical amplification.

(Other components)

The photosensitive resin composition of the present invention preferably contains other components.

The other components preferably contain a sensitizer and a development accelerator in view of sensitivity. Further, from the viewpoint of coating properties, a solvent is preferably contained, and from the viewpoint of physical properties of the film, a crosslinking agent is preferably contained.

From the standpoint of substrate adhesion, the photosensitive resin composition of the present invention preferably contains an adhesion improver. It is preferable that the photosensitive resin composition contains a basic compound from the viewpoint of liquid storage stability, and from the viewpoint of coating properties, the fluororesin surfactant and / It is preferable to contain a surfactant.

If necessary, the photosensitive resin composition of the present invention may further contain additives such as antioxidants, plasticizers, and heat radical generators, thermal acid generators, acid proliferators, ultraviolet absorbers, thickeners, A known additive may be added.

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

<Increase / decrease>

In the photosensitive resin composition of the present invention, in combination with the above-mentioned acid generator, it is preferable to add a sensitizer to accelerate the decomposition thereof. The sensitizer absorbs an actinic ray or radiation to become an electron-excited state. The sensitizer in the electron-excited state comes into contact with the acid generator to generate electron transfer, energy transfer, heat generation and the like. As a result, the acid generator generates a chemical change and decomposes to generate an acid.

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

Polynuclear aromatic compounds such as pyrene, perylene, triphenylene, anthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 3,7-dimethoxyanthracene, 9,10- Anthracene, xanthone, xanthone, thioxanthone, dimethylthioxanthone, diethylthioxanthone, and the like), xanthone Thiocarbons, thiocarbons, thiocarbons, thiocarbons, thiocarbons, thiocarbons, thiocarbons, thiocarbons, thiocarbons, (For example, thionine, methylene blue, toluidine blue), acridines (e.g., acridine orange, chloroflavin, acriflavine), acridones -Butyl-2-chloroacridone), anthraquinones (e.g., anthraquinone), squaryliums (e.g., squalium), styryls, (For example, 2- [2- [4- (dimethylamino) phenyl] ethenyl] benzoxazole), coumarins (for example, 7-diethylamino 4-methylcoumarin, Methylcoumarin, 2,3,6,7-tetrahydro-9-methyl-1H, 5H, 11H [l] benzopyrano [6,7,8-ij] quinolizine-11-pne). Among these sensitizers, a sensitizer having an electron-exciting state by absorbing an actinic ray or radiation to be in an electron-excited state and having an electron-transferring action to an acid generator is preferable, and polycyclic aromatic compounds, acridones, coumarins, And polycyclic aromatic compounds are more preferable. Of the polynuclear aromatics, anthracene derivatives are most preferred.

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 acid generator from the viewpoints of both sensitivity and transparency.

<Solvent>

The photosensitive resin composition of the present invention preferably contains a solvent.

It is preferable that the photosensitive resin composition of the present invention is produced as a solution in which a specific resin as an essential component and an acid generator and optional components of various additives as preferable components are dissolved in a solvent.

As the solvent to be used in the photosensitive 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 Propylene glycol monoalkyl ether ethers, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol Monoalkyl ether acetates, esters, ketones, amides, lactones, and the like.

Examples of the solvent used in the photosensitive resin composition of the present invention include (1) ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether ; (2) ethylene glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether and ethylene glycol dipropyl ether; (3) ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate and ethylene glycol monobutyl ether acetate; (4) propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether and propylene glycol monobutyl ether; (5) propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol monomethyl ether and diethylene glycol monoethyl ether;

(6) propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate and propylene glycol monobutyl ether acetate; (7) diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether and diethylene glycol ethyl methyl ether; (8) diethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate and diethylene glycol monobutyl ether acetate; (9) dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether and dipropylene glycol monobutyl ether; (10) dipropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether and dipropylene glycol ethyl methyl ether;

(11) dipropylene glycol monoalkyl ether acetates such as dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monopropyl ether acetate and dipropylene glycol monobutyl ether acetate; (12) Lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate, isobutyl lactate, isobutyl lactate, n-amyl lactate, and lactic acid / (13) A process for producing a compound represented by the following formula (1), wherein n is 1, Aliphatic carboxylic acid esters such as isobutyl propionate, methyl butyrate, ethyl butyrate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate and isobutyl butyrate; (14) A process for producing a compound represented by the above formula (1), which comprises dissolving at least one compound selected from the group consisting of ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy- 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, 3-methoxypropionyl acetate, 3-methoxypropionyl acetate, Methyl-3-methoxybutyl butyrate, methyl acetoacetate, ethyl acetoacetate, methyl pyruvate, and ethyl pyruvate;

(15) ketones such as methyl ethyl ketone, methyl propyl ketone, methyl n-butyl ketone, methyl isobutyl ketone, 2-heptanone, 3-heptanone, 4-heptanone and cyclohexanone; (16) amides such as N-methylformamide, N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide and N-methylpyrrolidone; (17) lactones such as? -Butyrolactone, and the like.

These solvents may also contain, if necessary, benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, caproic acid, Solvents such as 1-octanol, 1-nonanol, benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate and propylene carbonate may also be added.

Of the above solvents, particularly preferred are diethylene glycol ethyl methyl ether and propylene glycol monomethyl ether acetate.

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

The solvent which can be used in the present invention is preferably one type alone or in combination of two types, more preferably two kinds of solvents, more preferably propylene glycol monoalkyl ether acetates and diethylene glycol dialkyl ethers It is more preferable to use them in combination.

The content of the solvent in the photosensitive 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 specific resin.

(Development accelerator)

The photosensitive resin composition of the present invention preferably contains a development accelerator.

As the development accelerator, any compound having a phenomenon of promoting development may be used, but it is preferably a compound having at least one structure selected from the group consisting of a carboxy group, a phenolic hydroxyl group and an alkyleneoxy group, and a carboxy group or a phenolic hydroxyl group Is more preferable, and a compound having a phenolic hydroxyl group is most preferable.

The molecular weight of the development promoter is preferably 100 to 2000, more preferably 150 to 1500, and most preferably 150 to 1,000.

As examples of the development accelerator, those having an alkyleneoxy group include polyethylene glycol, monomethyl ether of polyethylene glycol, dimethyl ether of polyethylene glycol, polyethylene glycol glyceryl ester, polypropylene glycol glyceryl ester, polypropylene glycol diglyceryl ester , Polybutylene glycol, polyethylene glycol-bisphenol A ether, polypropylene glycol-bisphenol A ether, alkyl ether of polyoxyethylene, alkyl ester of polyoxyethylene, and compounds described in Japanese Patent Application Laid-Open No. 9-222724 .

Examples of compounds having a carboxyl group include compounds described in Japanese Patent Application Laid-Open Nos. 2000-66406, 9-6001, 10-20501, 11-338150, and the like.

Examples of those having a phenolic hydroxyl group include those disclosed in JP-A Nos. 2005-346024, 10-133366, 9-194415, 9-222724, 11-171810 Compounds described in JP-A-2007-121766, JP-A-9-297396, JP-A-2003-43679 and the like can be enumerated. Of these, phenol compounds having 2 to 10 benzene ring numbers are preferred, and phenol compounds having 2 to 5 benzene ring numbers are more favorable. Particularly preferred examples include phenolic compounds disclosed as dissolution accelerators in JP-A-10-133366.

The development accelerator may be used alone or in combination of two or more.

The amount of the development promoter (M) to be added to the photosensitive 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, And most preferably 0.5 to 10 parts by mass.

(Crosslinking agent)

The photosensitive resin composition of the present invention preferably contains a crosslinking agent, if necessary. By adding a crosslinking agent, the cured film obtained by the photosensitive resin composition of the present invention can be made into a stronger film.

As the crosslinking agent, for example, a compound having two or more epoxy groups or oxetanyl groups in the molecule described below, an alkoxymethyl group-containing crosslinking agent, or a compound having at least one ethylenically unsaturated double bond can be added.

Of these crosslinking agents, particularly preferred are compounds having two or more epoxy groups or oxetanyl groups in the molecule.

- a compound having two or more epoxy groups or oxetanyl groups in the molecule -

Specific examples of the compound having two or more epoxy groups in the molecule include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin and aliphatic epoxy resin.

These are available as commercial products. Examples of the bisphenol A epoxy resin include epoxy resins such as JER827, JER828, JER834, JER1001, JER1002, JER1003, JER1055, JER1007, JER1009, JER1010 (manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON860, EPICLON1050, EPICLON1051, EPICLON1055 JER4005, JER4007, JER4010 (manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON 830, EPICLON 835 (manufactured by DIC Corporation), and EPICLON 835 (manufactured by DIC Corporation), and the like. Examples of the bisphenol F type epoxy resin include JER806, JER807, JER4004, JER152, JER157S70, JER157S65 (above, manufactured by Japan Epoxy Resin Co., Ltd.) (trade name, manufactured by Nippon Kayaku Co., Ltd.), and the like can be used as the phenol novolak type epoxy resin. EPICLONN-740, EPICLONN-770 and EPICLONN-775 (manufactured by DIC Corporation), and EPICLONN-660, EPICLONN-665, EPICLONN-670 and EPICLONN- EPICLONN-690, EPICLONN-690 (manufactured by DIC Corporation), EOCN-1020 (manufactured by Nippon Kayaku Co., East E P-4085S, EP-4088S (manufactured by ADEKA), Suloxide 2021P, Suloxide 2081, Suloxide 2083, Suloxide 2085, EHPE3150, EPOLEADPB3600 and PB4700 (manufactured by Daicel Chemical Industries, And the like. In addition, ADEKARESINEP-4000S, EP-4003S, EP-4010S and EP-4011S (manufactured by ADEKA), NC-2000, NC-3000, NC-7300, XD- , EPPN-502 (manufactured by ADEKA Co., Ltd.), and the like. These may be used alone or in combination of two or more.

Among these, preferred are bisphenol A type epoxy resin, bisphenol F type epoxy resin, and phenol novolak type epoxy resin. Particularly, a bisphenol A type epoxy resin is preferable.

As specific examples of the compound having two or more oxetanyl groups in the molecule, Aromoxetane OXT-121, OXT-221, OX-SQ and PNOX (all manufactured by Doago Kosai Co., Ltd.) can be used.

The oxetanyl group-containing compound may be used alone or in combination with a compound containing an epoxy group.

The amount of the compound having two or more epoxy groups or oxetanyl groups in the molecule to be added to the photosensitive resin composition of the present invention is preferably 1 to 50 parts by mass, more preferably 3 to 30 parts by mass desirable.

- crosslinking agent containing an alkoxymethyl group -

As the alkoxymethyl group-containing crosslinking agent, alkoxymethylated melamine, alkoxymethylated benzoguanamine, alkoxymethylated glycoluril and alkoxymethylated urea are preferable. These are obtained by converting the methylol group of methylol melamine, methylol benzoguanamine, methylol glycoluryl or methylol group into an alkoxymethyl group, respectively. The kind of the alkoxymethyl group is not particularly limited, and examples thereof include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, and a butoxymethyl group. From the viewpoint of the amount of outgas generated, a methoxymethyl group .

Of these crosslinking compounds, alkoxymethylated melamine, alkoxymethylated benzoguanamine, and alkoxymethylated glycoluril are preferable crosslinking compounds, and from the viewpoint of transparency, alkoxymethylated glycoluril is particularly preferable.

These alkoxymethyl group-containing crosslinking agents are commercially available, for example, from Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156, 1158, 1123 , 1170, 1174, UFR65, 300 (manufactured by Mitsui Cyanamid), NIKARAK MX-750, -032, -706, -708, -40, -31, -270, -280, -290 , NIKARAK MS-11, NIKARAK MW-30HM, -100 LM, -390 (manufactured by SANWA CHEMICAL Co., Ltd.), and the like.

When an alkoxymethyl group-containing crosslinking agent is used in the photosensitive resin composition of the present invention, the amount of the alkoxymethyl group-containing crosslinking agent to be added is preferably 0.05 to 50 parts by mass, more preferably 0.5 to 10 parts by mass, per 100 parts by mass of the specific resin . The addition in this range provides a favorable alkali solubility at the time of development and excellent solvent resistance of the film after curing.

- a compound having at least one ethylenically unsaturated double bond -

As the compound having at least one ethylenic unsaturated double bond, a (meth) acrylate compound such as monofunctional (meth) acrylate, bifunctional (meth) acrylate or trifunctional or higher functional (meth) have.

Examples of the monofunctional (meth) acrylate include 2-hydroxyethyl (meth) acrylate, carbitol (meth) acrylate, isobornyl (meth) acrylate, 3-methoxybutyl Acrylate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, and the like.

Examples of the bifunctional (meth) acrylate include ethylene glycol (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol (meth) acrylate, polypropylene glycol Di (meth) acrylate, tetraethylene glycol di (meth) acrylate, bisphenoxyethanol fluorene diacrylate, and bisphenoxyethanol fluorene diacrylate.

Examples of trifunctional or higher (meth) acrylates include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri ((meth) acryloyloxyethyl) phosphate, pentaerythritol tetra (Meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.

These compounds having at least one ethylenic unsaturated double bond are used singly or in combination of two or more.

The proportion of the compound having at least one ethylenically unsaturated double bond in the photosensitive resin composition of the present invention is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, based on 100 parts by mass of the specific resin. By containing a compound having at least one ethylenically unsaturated double bond in such a ratio, the heat resistance and surface hardness of the cured film obtained from the photosensitive resin composition of the present invention can be improved. When a compound having at least one ethylenically unsaturated double bond is added, it is preferable to add a thermal radical generator described later.

(Adhesion improving agent)

The photosensitive resin composition of the present invention preferably contains an adhesion improver.

The adhesion improver that can be used in the photosensitive resin composition of the present invention is an adhesion improver that improves the adhesion between an inorganic substance to be a substrate such as a silicon compound such as silicon, silicon oxide, or silicon nitride, a metal such as gold, copper, . Specific examples thereof include silane coupling agents and thiol compounds. The silane coupling agent used as the adhesion improver used in the present invention is not specifically limited, and any known silane coupling agent may be used for the purpose of modifying the interface.

Preferable silane coupling agents include, for example,? -Aminopropyltrimethoxysilane,? -Aminopropyltriethoxysilane,? -Glycidoxypropyltrialkoxysilane,? -Glycidoxypropylalkyldialkoxysilane,? -Methacryloxypropyltrialkoxysilane,? -Methacryloxypropylalkyldialkoxysilane,? -Chloropropyltrialkoxysilane,? -Mercaptopropyltrialkoxysilane,? - (3,4-epoxycyclohexyl) ethyl tri Alkoxysilane, 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. These are effective for improving the adhesion with the substrate, and are also effective for adjusting the taper angle with the substrate.

The content of the adhesion improver in the photosensitive 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 specific resin.

(Basic compound)

The photosensitive resin composition of the present invention preferably contains a basic compound.

As the basic compound, any of those used as a chemically amplified resist may 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 aliphatic amines such as 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 heterocyclic amines include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, Benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinamide, quinoline, 8- 4-methyl morpholine, 1,5-diazabicyclo [4.3.0] -5-nonene, pyrrolidine, piperidine, piperazine, morpholine, 1,8-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. have.

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 which can be used in the present invention may be used singly or in combination of two or more kinds. However, two or more kinds of basic compounds are preferably used, more preferably two kinds of basic compounds, More preferably in combination.

The content of the basic compound in the photosensitive 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 with respect to 100 parts by mass of the specific resin.

(Surfactants)

The photosensitive resin composition of the present invention preferably contains a surfactant.

As the surfactant, any of anionic, cationic, nonionic or amphoteric surfactants can be used, but preferred surfactants are nonionic surfactants.

Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone surfactants, and fluorine surfactants.

Examples of the surfactant include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Goeisha Chemical Co., Ltd.), F-top (manufactured by JEMCO), Megapack (manufactured by DIC Corporation) (Manufactured by Asahi Glass Co., Ltd.), PolyFox (manufactured by OMNOVA), and the like can be given.

As the surfactant, a copolymer (3) containing the repeating unit A and the repeating unit B shown below may be mentioned as a preferable example. The weight average molecular weight (Mw) of the copolymer is 1000 or more and 10000 or less, preferably 1500 or more and 5000 or less. The weight average molecular weight is a value in terms of polystyrene measured by gel permeation chromatography.

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 is an integer of not less than 10 mass% and not more than 80 mass%, q is not less than 20 mass% And n represents an integer of 1 or more and 10 or less.

L in the repeating unit B is preferably an alkylene group represented by the following general formula (4).

In the general formula (4), R ²⁵ represents an alkyl group having 1 to 4 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability to a surface to be coated, desirable.

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

Examples of the fluorine-based surfactant and the silicon-based surfactant include those described in Japanese Patent Application Laid-Open Nos. 62-36663, 61-226746, 61-226745, 62-170950, 63- Surfactants such as those disclosed in the respective publications such as JP-A No. 34540, JP-A No. 7-230165, JP-A No. 8-62834, JP-A No. 9-54432, JP-A No. 9-5988, And a commercially available surfactant may be used.

(Commercially available from Shin-Akita Kasei Co., Ltd.), Fluorad FC430 and 431 (manufactured by Sumitomo-3M Co., Ltd.), Megafac F171 , F173, F176, F189 and R08 (manufactured by DIC Corporation), SURFON S-382, SC101, 102, 103, 104, 105 and 106 (manufactured by Asahi Glass Co., Ltd.), PolyFox series (OMNOVA (Trade name, manufactured by Shimadzu Corporation), and silicone surfactants. 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 silicon-based surfactant may be used in combination.

The total amount of the surfactant to be added to the photosensitive resin composition of the present invention is preferably 10 parts by mass or less, more preferably 0.01 to 10 parts by mass, more preferably 0.01 to 1 part by mass relative to 100 parts by mass of the specific resin desirable.

(Antioxidant)

The photosensitive resin composition of the present invention may contain an antioxidant. As the antioxidant, a known antioxidant may be contained. By adding an antioxidant, coloration of the cured film can be prevented, or film thickness reduction due to decomposition can be reduced, and furthermore, there is an advantage of excellent heat-resistant transparency.

Examples of such antioxidants include phosphorus antioxidants, hydrazides, hindered amine antioxidants, sulfur antioxidants, phenol antioxidants, ascorbic acids, zinc sulfate, sugars, nitrite, sulfite, thiosulfate, And a hydroxyamine derivative. Among them, 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 alone or in combination of two or more.

Examples of commercially available products of phenolic antioxidants include adecastab AO-60, adecastab AO-80 (manufactured by ADEKA), and Irganox 1098 (manufactured by BASF Corporation) .

The content of the antioxidant is preferably 0.1 to 6% by mass, more preferably 0.2 to 5% by mass, and particularly preferably 0.5 to 4% by mass, based on the total solid content of the photosensitive resin composition. When the content is in this range, sufficient transparency of the formed film can be obtained and sensitivity at the time of pattern formation can be improved.

As the additives other than the antioxidant, various ultraviolet absorbers, metal deactivators, and the like described in "New developments of the polymer additive " (Ilgan Kogyo Shimbun) may be added to the photosensitive resin composition of the present invention.

(Plasticizer)

The photosensitive resin composition of the present invention may contain a plasticizer.

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

The content of the plasticizer in the photosensitive resin composition of the present invention is preferably 0.1 to 30 parts by mass, more preferably 1 to 10 parts by mass, per 100 parts by mass of the specific resin.

(Thermal radical generator)

The photosensitive resin composition of the present invention may contain a thermal radical generator and may contain an ethylenically unsaturated compound such as a compound having at least one ethylenically unsaturated double bond as described above and may contain a thermal radical generator desirable.

As the thermal radical generator in the present invention, a known thermal radical generator may be used.

The thermal radical generator is a compound that generates radicals by heat energy to initiate or promote the polymerization reaction of the polymerizable compound. The addition of the thermal radical generator makes the resulting cured film stronger, which may improve heat resistance and solvent resistance.

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, A compound having a bond, an azo-based compound, and a non-benzyl compound.

One kind of thermal radical generator may be used alone, or two or more kinds of thermal radical generators may be used in combination.

The content of the heat radical generator in the photosensitive resin composition of the present invention is preferably from 0.01 to 50 parts by mass, more preferably from 0.1 to 20 parts by mass, more preferably from 0.1 to 20 parts by mass, based on 100 parts by mass of the specific resin, And most preferably 0.5 to 10 parts by mass.

(Thermal acid generator)

In the present invention, a thermal acid generator may be used in order to improve physical properties of the film in low-temperature curing.

The thermal acid generator of the present invention is a compound which generates acid by heat and is generally a compound having a thermal decomposition point in the range of 130 to 250 캜, preferably 150 to 220 캜, for example, (Low nucleophilic) acid such as carboxylic acid, disulfonylimide and the like.

The generated acid is preferably a strong alkyl or aryl carboxylic acid having a pKa of 2 or less and substituted by a sulfonic acid or an electron attracting group, or a disulfonyl imide substituted with an electron attracting group. Examples of the electron-withdrawing group include a halogen atom such as F atom, a haloalkyl group such as trifluoromethyl group, a nitro group, and a cyano group.

In the present invention, it is also preferable to use a sulfonic acid ester which generates an acid by heat without substantially generating an acid by irradiation with exposure light.

It can be judged that there is no change in the spectrum by the IR spectrum and the NMR spectrum measurement before and after exposure of the compound, in which substantially no acid is generated by the irradiation of the exposure light.

The molecular weight of the sulfonic acid ester is generally 230 to 1000, preferably 230 to 800.

The sulfonic acid ester usable in the present invention may be a commercially available sulfonic acid ester or may be synthesized by a known method. The sulfonic acid ester can be synthesized, for example, by reacting a sulfonyl chloride or a sulfonic acid anhydride with a corresponding polyhydric alcohol under basic conditions.

The content of the sulfonic acid ester in the photosensitive resin composition is preferably 0.5 to 20 parts by mass, more preferably 1 to 15 parts by mass, based on 100 parts by mass of the specific resin.

(Acid proliferating agent)

In the photosensitive resin composition of the present invention, an acid propagating agent may be used for the purpose of improving the sensitivity. The acid-proliferating agent used in the present invention is a compound capable of generating an acid by the acid catalysis reaction to increase the concentration of the acid in the reaction system, and is a compound stably present in the absence of acid. Such a compound accelerates the reaction with the progress of the reaction because one or more acids increase in a single reaction. However, since the generated acid itself induces self-decomposition, the intensity of the acid generated here Is preferably 3 or less, more preferably 2 or less, as the acid dissociation constant, pKa.

Specific examples of acid proliferating agents include those described in Japanese Patent Laid-Open Nos. 10-1508 [0203] to 0223, Japanese Patent Laid-Open Nos. 10-282642 [0016] to 0055, and Japanese Patent Laid- Page 12 to page 47, line 2.

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

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

&Lt; Method of forming a cured film &

Next, a method of forming the cured film of the present invention will be described.

The method for forming a cured film of the present invention is characterized by including the following steps (1) to (5).

(1) a coating step of applying the photosensitive resin composition of the present invention on a substrate

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

(3) an exposure process for exposing the applied photosensitive resin composition by an actinic ray

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

(5) a post-baking step of thermally curing the developed photosensitive resin composition

In the method for forming a cured film of the present invention, after the exposure in the exposure step, the development step (4) may be performed without performing the heat treatment.

Further, before the post-baking step, (6) the step of exposing the developed photosensitive resin composition to the entire surface may be further included.

Each step will be described below in order.

(1), the photosensitive resin composition of the present invention is applied onto a substrate to form a wet film containing a solvent.

In the solvent removing step (2), the solvent is removed from the coated film by reduced pressure (vacuum) and / or heating to form a dried coating film on the substrate.

In the exposure step of (3), an active ray having a wavelength of 300 nm or more and 450 nm or less is irradiated to the obtained coating film. In this step, the acid generator (B) is decomposed to generate acid. The acid-decomposable groups in the structural units (a1) and (a2) contained in the specific resin are decomposed by the catalytic action of the generated acid to generate a carboxyl group and / or a phenolic hydroxyl group.

In order to accelerate the decomposition reaction in the region where the acid catalyst is produced, PEB (Post Exposure Bake: post-exposure heat treatment) may be performed as necessary. With PEB, the generation of a carboxyl group and / or a phenolic hydroxyl group from an acid-decomposable group can be promoted.

The acid-decomposable group in the structural unit (a1) and the structural unit (a2) in the present invention has a low activation energy for acid decomposition and is easily decomposed by an acid derived from an acid generator by exposure to give a carboxyl group and / It is not always necessary to perform PEB because it generates a hydroxyl group. Therefore, after the exposure process of (3), a positive image can be formed by performing development in the developing process of (4) without performing PEB.

In addition, by performing PEB at a relatively low temperature, the decomposition of the acid decomposable group can be accelerated without causing a crosslinking reaction. The temperature for PEB 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.

(4), a specific resin having a liberated carboxyl group is developed using an alkaline developer. A positive image is formed by removing the exposed region containing a photosensitive resin composition having a carboxyl group and / or a phenolic hydroxyl group which is easily soluble in an alkaline developer.

(A1) and the structural unit (a2) by thermal decomposition of the acid-decomposable group in the structural unit (a3) by heating the obtained positive image in the post-baking step of the structural unit (5) By crosslinking with an epoxy group and / or an oxetanyl group, a cured film can be formed. This heating is preferably performed at a high temperature of 150 ° C or higher, more preferably 180 ° C to 250 ° C, and particularly preferably 200 ° C to 250 ° C. The heating time can be appropriately set according to the heating temperature and the like, but it is preferably within a range of 10 to 90 minutes.

(6) a step of exposing the developed photosensitive resin composition before the post-baking step. More preferably, the step of irradiating the pattern of the developed photosensitive resin composition with an actinic ray, preferably ultraviolet light, The crosslinking reaction can be promoted by an acid generated by irradiation of a light ray.

Next, a method for forming a cured film using the photosensitive resin composition of the present invention will be described in detail.

[Method for producing photosensitive resin composition]

A solvent is optionally mixed with an essential component of a specific resin and an acid generator in a predetermined ratio and optionally in an optional manner, followed by stirring and dissolution to prepare a photosensitive resin composition. For example, a photosensitive resin composition may be prepared by preparing a solution in which a specific resin or acid generator is dissolved in each solvent in advance, and mixing them in a predetermined ratio. The solution of the photosensitive resin composition prepared as described above may be used after being filtered using a filter having a pore size of 0.1 탆 or the like.

An example of a preferred embodiment of the photosensitive resin composition of the present invention is a photosensitive resin composition containing a specific resin in a range of 60 to 95 mass% based on the total solid content of the photosensitive resin composition, and an acid generator in a range of 0.1 to 10 mass% .

Another example of preferred embodiments of the photosensitive resin composition of the present invention is a photosensitive resin composition containing a specific resin in a range of 40 mass% to 70 mass% relative to the total solid content of the photosensitive resin composition, 0.1 to 10 mass By mass, and further contains a crosslinking agent in a range of 3% by mass to 40% by mass.

<Coating Process and Solvent Removal Process>

The desired dry film can be formed by applying the photosensitive resin composition to a predetermined substrate and removing the solvent by reduced pressure and / or heating (prebaking). Examples of the substrate include a polarizing plate, a glass plate provided with a black matrix layer and a color filter layer as necessary, and a transparent conductive circuit layer provided thereon, for example, in the production of a liquid crystal display device. The coating method on the substrate is not particularly limited, and for example, a slit coating method, a spray method, a roll coating method, and a spin coating method can be used. Among them, the slit coating method is preferable from the viewpoint of being suitable for a large substrate. Here, a large substrate refers to a substrate having a size of 1 m or more on each side.

The heating condition of the solvent removal step (2) is such that the acid decomposable group decomposes in the structural unit (a1) and / or the structural unit (a2) in the specific resin in the unexposed portion and the specific resin is dissolved in an alkali developer But it is preferably from 70 to 120 DEG C for about 30 seconds to 300 seconds, although it varies depending on the kind of each component and blending ratio.

<Exposure Step>

(3) In the exposure step, the substrate provided with the dried coating film of the photosensitive resin composition is irradiated with a predetermined pattern of actinic rays. The exposure may be performed via a mask, or a predetermined pattern may be directly drawn. An active ray having a wavelength of 300 nm or more and 450 nm or less can be preferably used. After the exposure process, PEB is performed if necessary.

A low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, an LED light source, a chemical lamp, a laser generator, or 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), h-line (405 nm) 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, 343 nm and 355 nm are used for the solid-state (YAG) laser, 351 nm (XeF) is used for the excimer laser, and 375 nm and 405 nm are used for the semiconductor laser. Of these, 355 nm and 405 nm are more preferable in terms of stability and cost. The laser can be irradiated onto the coating film by dividing it into one or a plurality of circuits.

Energy density per one pulse of the laser is preferably 0.1mJ / cm ² or more 10000mJ / cm ² or less. In order to sufficiently cure the coating film, 0.3mJ / cm ² or more is more preferable, and 0.5mJ / cm ² or more to the coating film so as not to break down by the most preferred, and ablation (ablation) phenomenon, 1000mJ / cm ² Or less, and most preferably 100 mJ / cm ² or less.

The pulse width is preferably from 0.1 nsec to 30000 nsec. More preferably not less than 0.5 nsec, most preferably not less than 1 nsec, and more preferably not more than 1000 nsec, more preferably not more than 50 nsec, in order to improve the alignment accuracy at the time of scanning exposure, in order to prevent decomposition of the color coating film by the ablation phenomenon Most preferred.

The frequency of the laser is preferably 1 Hz to 50000 Hz, more preferably 10 Hz to 1000 Hz.

In order to shorten the exposure processing time, the frequency of the laser is more preferably 10 Hz or more, most preferably 100 Hz or more, and more preferably 10000 Hz or less and 1000 Hz or less Most preferred.

The laser is preferable to the mercury lamp in that it is easy to narrow the focus, and a mask for pattern formation in the exposure process is unnecessary and cost can be reduced.

Examples of the exposure apparatus that can be used in the present invention include, but are not limited to, commercially available products such as Callisto (manufactured by V-Technology Corporation), AEGIS (manufactured by V Technology Corporation), DF2200G (manufactured by Dainippon Screen, ) Can be used. Other devices than the above are also used for convenience.

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

<Development Process>

(4) In the developing process, an exposed pattern area is removed by using a basic developing solution to form an image pattern. Examples of the basic compound used in the developer include alkali metal hydroxide such as lithium hydroxide, sodium hydroxide, potassium hydroxide and the like; 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 usually 30 to 180 seconds, and the developing method may be any of a liquid method, a dipping method, and a shower method. After the development, a desired pattern can be formed by conducting water washing for 10 to 90 seconds.

&Lt; Post baking step (crosslinking step) >

For a predetermined time at a predetermined temperature, for example, 180 to 250 캜 for a predetermined time, for example, on a hot plate, using a heating apparatus such as a hot plate or an oven for a pattern corresponding to the unexposed region obtained by development And the acidic decomposable group in the specific resin is decomposed to generate a carboxyl group and / or a phenolic hydroxyl group by performing a heat treatment for 30 minutes to 90 minutes in the case of an oven and a crosslinking reaction in the presence of an epoxy group and / or an oxetanyl group By reacting with the genital organs and crosslinking, a protective film or an interlayer insulating film excellent in heat resistance, hardness and the like can be formed. In addition, transparency can be improved by performing the heat treatment in a nitrogen atmosphere.

Further, before the heat treatment, the substrate on which the pattern is formed is re-exposed by the action of an actinic ray, and then subjected to post-baking (re-exposure / post-baking) to remove acid from the acid generator (B) And functions as a catalyst for promoting crosslinking.

That is, the method for forming a cured film in the present invention preferably includes the above-described step (6) for re-exposure by an actinic ray between the developing step and the post-baking step.

The exposure in the re-exposure step may be performed by the same means as in the exposure step, but in the re-exposure step, it is preferable to perform the entire exposure on the side of the substrate where the film is formed by the photosensitive resin composition of the present invention. The preferable exposure amount of the re-exposure step is 100 to 1,000 mJ / cm &lt; ^{2 &} gt ;.

With the photosensitive resin composition of the present invention, a cured film having a high sensitivity, suppressing the generation of residues during development, and having a surface with excellent smoothness is obtained, and the cured film is useful as an interlayer insulating film. The interlayer insulating film formed using the photosensitive resin composition of the present invention has high transparency and can form a pattern of a good shape and also has excellent smoothness of its surface. Therefore, the organic EL display device, the liquid crystal display device Lt; / RTI &gt;

The organic EL display device or liquid crystal display device to which the photosensitive composition of the present invention can be applied is not particularly limited except that the cured film formed using the photosensitive resin composition of the present invention is used as a planarizing film or an interlayer insulating film, And various known organic EL display devices and liquid crystal display devices having various structures.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a structural conceptual diagram showing an example of an organic EL display device using the photosensitive resin composition of the present invention. FIG. 1 is a schematic cross-sectional view of a substrate in a bottom emission type organic EL display device, and has a planarization film 4.

A bottom gate type TFT 1 is formed on a glass substrate 6 and an insulating film 3 made of Si ₃ N ₄ is formed so as to cover the TFT 1. A wiring 2 (height 1.0 mu m) connected to the TFT 1 via the contact hole is formed on the insulating film 3 after forming a contact hole (not shown) in the insulating film 3. The wiring 2 is for connecting the organic EL element formed in the TFT 1 or in a subsequent step to the TFT 1. [

The flattening film 4 is formed on the insulating film 3 in a state of embedding (embedding) irregularities by the wiring 2 in order to planarize the irregularities formed by the formation of the wiring 2.

On the planarizing film 4, a bottom-emission organic EL element is formed. That is, a first electrode 5 made of ITO is formed on the planarization film 4 by being connected to the wiring 2 through the contact hole 7. The first electrode 5 corresponds to the anode of the organic EL element.

An insulating film 8 is formed so as to cover the periphery of the first electrode 5. By providing the insulating film 8, a short circuit is formed between the first electrode 5 and the second electrode formed in the subsequent steps .

Although not shown in Fig. 1, a hole transport layer, an organic luminescent layer, and an electron transport layer are sequentially deposited by evaporation through a desired pattern mask. Next, a second electrode made of Al is formed on the entire upper surface of the substrate, An organic EL display device of an active matrix type in which a glass plate and an ultraviolet curable epoxy resin are used for sealing to each other and the TFT 1 for driving each organic EL element is connected is obtained.

2 is a conceptual cross-sectional view showing an example of the liquid crystal display device 10 of the active matrix type. This color liquid crystal display device 10 is a liquid crystal panel having a backlight unit 12 on its back surface and the liquid crystal panel corresponds to all the pixels disposed between two glass substrates 14 and 15 to which a polarizing film is pasted The element of the TFT 16 is disposed. In each element formed on the glass substrate, an ITO transparent electrode 19 for forming a pixel electrode is wired through a contact hole 18 formed in the cured film 17. On the ITO transparent electrode 19, an RGB color filter 22 in which a layer of the liquid crystal 20 and a black matrix are arranged is provided.

[Example]

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

Synthetic examples of specific resins A to U, comparative resins R1 to 11, and acid generators B5 to B8 used in Examples and Comparative Examples are shown below.

The abbreviations of the respective compounds used in the synthesis examples of the following specific resins A to U represent the following compounds, respectively.

MAA: methacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.)

MAEVE: 1-ethoxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)

OXE-30: 3-ethyl-3-oxetanylmethyl methacrylate (manufactured by Osaka Yuki Kagaku Kogyo Co., Ltd.)

HEMA: hydroxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)

V-65: 2,2'-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.)

EtMA: Ethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)

HMA: hexyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)

GMA: glycidyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)

St: Styrene (manufactured by Wako Pure Chemical Industries, Ltd.)

CMI: N-cyclohexylmaleimide (manufactured by Wako Pure Chemical Industries, Ltd.)

StOEVE: 4- (1-ethoxyethyloxy) styrene (synthetic)

DCPM: dicyclopentanyl methacrylate (FA-511A, manufactured by Hitachi Chemical)

MMA: methyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)

PGMEA: Methoxypropyl acetate (manufactured by Showa Denko)

HS-EDM: Hyosolve EDM (manufactured by Tohoku Kagaku Kogyo Co., Ltd.)

MATHF: 2-Tetrahydrofuranyl methacrylate (Synthesis)

MAEVE and StOEVE were synthesized in the same manner as the synthesis of MATHF shown below.

Synthesis of tetrahydro-2H-furan-2-yl methacrylate (MATHF)

Methacrylic acid (86 g, 1 mol) was cooled to 15 DEG C and camphorsulfonic acid (4.6 g, 0.02 mol) was added. To the solution, 2-dihydrofuran (71 g, 1 mol, 1.0 equivalent) was added dropwise. After stirring for 1 hour, saturated sodium hydrogencarbonate (500 mL) was added. The mixture was extracted with ethyl acetate (500 mL) and dried over magnesium sulfate. The insoluble material was filtered off and concentrated under reduced pressure at 40 ° C or lower. 125 g of tetrahydro-2H-furan-2-yl methacrylate (MATHF) having a boiling point (bp.) Of 54 to 56 캜 / 3.5 mmHg remained as a colorless oil (yield 80%).

&Lt; Synthesis Example 1: Synthesis of Specific Resin A >

HS-DEM (35.7 g) was placed in a three-necked flask, and the temperature was raised to 70 占 폚 in a nitrogen atmosphere. To this solution was added HS-EDM (35.7 g), MAA (1.72 g), MAEVE (12.65 g), OXE-30 (11.05 g), HEMA (5.20 g), V- And the solution was added dropwise over 2 hours. After completion of dropwise addition, stirring was performed for 4 hours to terminate the reaction. Thus, a specific resin A was obtained (acid value = 36.63, I / O value = 0.660). The weight average molecular weight was 6600.

&Lt; Synthesis Example 2: Synthesis of Specific Resin B) >

PGMEA (35.7 g) was placed in a three-necked flask, and the temperature was raised to 70 占 폚 in a nitrogen atmosphere. To this solution was added MAA (1.03 g), MAEVE (12.65 g), OXE-30 (12.52 g), HEMA (5.20 g), V-65 (3.47 g, 7 mol% based on monomer) dissolved in PGMEA And dropped for 2 hours. After completion of dropwise addition, stirring was performed for 4 hours to terminate the reaction. As a result, a specific resin B was obtained (acid value = 21.43, I / O value = 0.623). The weight average molecular weight was 7100.

&Lt; Synthesis Example 3: Synthesis of Specific Resin C >

HS-DEM (34.25 g) was placed in a three-necked flask, and the temperature was elevated to 70 占 폚 in a nitrogen atmosphere. To this solution was added HS-EDM (34.25 g), MAA (3.27 g), MAEVE (12.65 g), OXE-30 (12.52 g), HEMA (2.86 g), V- And the solution was added dropwise over 2 hours. After completion of dropwise addition, stirring was performed for 4 hours to terminate the reaction. As a result, a specific resin C was obtained (acid value = 71.45, I / O value = 0.670). The weight average molecular weight was 6900.

&Lt; Synthesis Example 4: Synthesis of Specific Resin D >

HS-DEM (36.0 g) was placed in a three-necked flask, and the temperature was raised to 70 占 폚 in a nitrogen atmosphere. HS-EDM (36.0 g) was added to the solution, MAA (0.51 g), MAEVE (12.65 g), OXE-30 (11.05 g), HEMA (7.03 g), V- And the solution was added dropwise over 2 hours. After completion of dropwise addition, stirring was performed for 4 hours to terminate the reaction. As a result, a specific resin D was obtained (acid value = 10.77, I / O value = 0.653). The weight average molecular weight was 7,000.

&Lt; Synthesis Example 5: Synthesis of Specific Resin E >

HS-DEM (34.5 g) was placed in a three-necked flask, and the temperature was raised to 70 占 폚 in a nitrogen atmosphere. To this solution was added HS-EDM (34.5 g), MAA (3.78 g), MAEVE (12.65 g), OXE-30 (11.05 g), HEMA (2.68 g), V- And the solution was added dropwise over 2 hours. After completion of dropwise addition, stirring was performed for 4 hours to terminate the reaction. As a result, a specific resin E was obtained (acid value = 83.47, I / O value = 0.673). The weight average molecular weight was 6800.

&Lt; Synthesis Example 6: Synthesis of Specific Resin F >

HS-DEM (33.5 g) was put in a three-necked flask, and the temperature was raised to 70 占 폚 in a nitrogen atmosphere. HS-EDM (33.5 g) was added to the solution, MAA (4.64 g), MAEVE (12.65 g), OXE-30 (11.05 g), HEMA (0.78 g), V- And the solution was added dropwise over 2 hours. After completion of dropwise addition, stirring was performed for 4 hours to terminate the reaction. Thus, a specific resin F was obtained (acid value = 103.98, I / O value = 0.679). The weight average molecular weight was 8,400.

&Lt; Synthesis Example 7: Synthesis of Specific Resin G >

HS-DEM (34.0 g) was placed in a three-neck flask, and the temperature was raised to 70 占 폚 in a nitrogen atmosphere. To this solution was added HS-EDM (34.0 g) MAA (1.54 g), MAEVE (10.44 g), OXE-30 (7.73 g), HEMA (9.63 g), V- And the solution was added dropwise over 2 hours. After completion of dropwise addition, stirring was performed for 4 hours to terminate the reaction. As a result, a specific resin G was obtained (acid value = 34.40, I / O value = 0.792). The weight average molecular weight was 7200.

&Lt; Synthesis Example 8: Synthesis of Specific Resin H >

HS-DEM (34.0 g) was placed in a three-neck flask, and the temperature was raised to 70 占 폚 in a nitrogen atmosphere. To the solution was added MAA (1.72 g), MAEVE (9.49 g), OXE-30 (7.36 g), HEMA (5.20 g), St (2.08 g), CMI (3.58 g), V- Was dissolved in HS-EDM (34.0 g) and added dropwise over 2 hours. After completion of dropwise addition, stirring was performed for 4 hours to terminate the reaction. As a result, a specific resin H was obtained (acid value = 38.10, I / O value = 0.657). The weight average molecular weight was 6800.

Synthesis Example 9: Synthesis of Specific Resin I &gt;

HS-DEM (36.5 g) was placed in a three-necked flask, and the temperature was raised to 70 占 폚 in a nitrogen atmosphere. HS-EDM (36.5 g) was added to the solution, MAA (1.72 g), StOEVE (11.53 g), OXE-30 (9.21 g), HEMA (9.11 g), V- And the solution was added dropwise over 2 hours. After completion of dropwise addition, stirring was performed for 4 hours to terminate the reaction. As a result, a specific resin I was obtained (acid value = 35.54, I / O value = 0.625). The weight average molecular weight was 9200.

&Lt; Synthesis Example 10: Synthesis of Specific Resin J >

HS-DEM (32.5 g) was placed in a three-necked flask, and the temperature was raised to 70 캜 under a nitrogen atmosphere. To the solution was added MAA (2.97 g), MAEVE (15.81 g), OXE-30 (3.68 g), MMA (3.60 g), DCPM (2.20 g), V- -EDM (32.5 g) and added dropwise over 2 hours. After completion of dropwise addition, stirring was performed for 4 hours to terminate the reaction. As a result, a specific resin J was obtained (acid value = 67.56, I / O value = 0.612). The weight average molecular weight was 8800.

&Lt; Synthesis Example 11: Synthesis of Specific Resin K >

HS-DEM (32.0 g) was placed in a three-necked flask, and the temperature was raised to 70 캜 in a nitrogen atmosphere. To this solution was added HS-EDM (32.0 g), MAA (2.92 g), MAEVE (10.44 g), OXE-30 (9.21 g), MMA (5.00 g), V- And the solution was added dropwise over 2 hours. After completion of dropwise addition, stirring was performed for 4 hours to terminate the reaction. As a result, a specific resin K was obtained (acid value = 69.16, I / O value = 0.615). The weight average molecular weight was 6900.

&Lt; Synthesis Example 12: Synthesis of Specific Resin L >

HS-DEM (32.5 g) was placed in a three-necked flask, and the temperature was raised to 70 캜 under a nitrogen atmosphere. To this solution was added MAA (1.72 g), MAEVE (12.65 g), GMA (11.37 g), HEMA (2.60 g) and V-65 (3.47 g, 7 mol% based on monomer) dissolved in 32.5 g of HS-EDM And dropped for 2 hours. After completion of dropwise addition, stirring was performed for 4 hours to terminate the reaction. Thus, a specific resin L was obtained (acid value = 39.58, I / O value = 0.693). The weight average molecular weight was 7600.

&Lt; Synthesis Example 13: Synthesis of Specific Resin M >

HS-DEM (31.0 g) was placed in a three-necked flask, and the temperature was raised to 70 캜 under a nitrogen atmosphere. To the solution, MAA (4.30 g), MAEVE (15.81 g), HEMA (6.50 g) and V-65 (3.47 g, 7 mol% based on monomer) were dissolved in 31.0 g of HS-EDM, did. After completion of dropwise addition, stirring was performed for 4 hours to terminate the reaction. By this, n1 was obtained. The weight average molecular weight was 6500.

Further, HS-DEM (33.5 g) was placed in a three-necked flask, and the temperature was raised to 70 캜 under a nitrogen atmosphere. To this solution, MAEVE (10.54 g), HEMA (4.33 g), GMA (14.21 g) and V-65 (3.47 g, 7 mol% based on monomer) were dissolved in 33.5 g of HS- And added. After completion of dropwise addition, stirring was performed for 4 hours to terminate the reaction. Thereby obtaining n2. The weight average molecular weight was 6700. (acid value = 39.92, I / O value = 0.757) by mixing n1 / n2 = 4/6 (mass ratio).

&Lt; Synthesis Example 14: Synthesis of Specific Resin N >

HS-DEM (31.0 g) was placed in a three-necked flask, and the temperature was raised to 70 캜 under a nitrogen atmosphere. To the solution, MAA (4.30 g), MAEVE (15.81 g), HEMA (6.50 g) and V-65 (3.47 g, 7 mol% based on monomer) were dissolved in 31.0 g of HS-EDM, did. After completion of dropwise addition, stirring was performed for 4 hours to terminate the reaction. I got o1 by it. The weight average molecular weight was 7200.

Further, HS-DEM (38.5 g) was placed in a three-necked flask, and the temperature was raised to 70 占 폚 in a nitrogen atmosphere. To the solution was dissolved 38.5 g of HS-EDM (10.54 g), HEMA (4.33 g), OXE-30 (18.42 g), V-65 (3.47 g, 7 mol% It took time to load. After completion of dropwise addition, stirring was performed for 4 hours to terminate the reaction. I got o2 by it. The weight average molecular weight was 6800. (acid value = 36.63, I / O value = 0.660) by mixing them at a ratio o1 / o2 = 4/6 (mass ratio).

&Lt; Synthesis Example 15: Synthesis of Specific Resin O >

HS-DEM (32.5 g) was placed in a three-necked flask, and the temperature was raised to 70 캜 under a nitrogen atmosphere. To this solution was added HS-EDM (32.5 g), MAA (3.44 g), HEMA (6.50 g), MAEVE (9.49 g), OXE-30 (9.21 g), V- And the solution was added dropwise over 2 hours. After completion of dropwise addition, stirring was performed for 4 hours to terminate the reaction. As a result, a specific resin O was obtained (acid value = 78.33, I / O value = 0.792). The weight average molecular weight was 8,100.

Synthesis Example 16: Synthesis of Specific Resin P &gt;

HS-DEM (33.0 g) was placed in a three-necked flask, and the temperature was raised to 70 占 폚 in a nitrogen atmosphere. To this solution was added HS-EDM (33.0 g), MAA (3.78 g), HEMA (5.98 g), MAEVE (9.49 g), OXE-30 (9.21 g), V- And the solution was added dropwise over 2 hours. After completion of dropwise addition, stirring was performed for 4 hours to terminate the reaction. Thus, a specific resin P was obtained (acid value = 86.70, I / O value = 0.795). The weight average molecular weight was 6900.

&Lt; Synthesis Example 17: Synthesis of Specific Resin Q >

HS-DEM (35.0 g) was placed in a three-necked flask, and the temperature was raised to 70 占 폚 in a nitrogen atmosphere. To this solution, MAA (3.96 g), MAEVE (12.65 g), OXE-30 (13.63 g) and V-65 (3.47 g, 7 mol% based on monomer) were dissolved in HS-EDM (35.0 g) I dropped it. After completion of dropwise addition, stirring was performed for 4 hours to terminate the reaction. Thereby, a specific resin Q was obtained (acid value = 85.33, I / O value = 0.614). The weight average molecular weight was 6500.

&Lt; Synthesis Example 18: Synthesis of Specific Resin R >

HS-DEM (33.0 g) was placed in a three-necked flask, and the temperature was raised to 70 占 폚 in a nitrogen atmosphere. To this solution, MAA (4.99 g), MAEVE (3.16 g), OXE-30 (22.47 g) and V-65 (3.47 g, 7 mol% based on monomer) were dissolved in HS-EDM (33.0 g) I dropped it. After completion of dropwise addition, stirring was performed for 4 hours to terminate the reaction. As a result, a specific resin R was obtained (acid value = 106.24, I / O value = 0.622). The weight average molecular weight was 6900.

&Lt; Synthesis Example 19: Synthesis of Specific Resin S) >

HS-DEM (32.5 g) was placed in a three-necked flask, and the temperature was raised to 70 캜 under a nitrogen atmosphere. To this solution was added HS-EDM (32.5 g), MAA (4.65 g), HEMA (4.69 g), MAEVE (7.91 g), OXE-30 (11.65 g), V- And the solution was added dropwise over 2 hours. After completion of dropwise addition, stirring was performed for 4 hours to terminate the reaction. As a result, a specific resin S was obtained (acid value = 107.08, I / O value = 0.791). The weight average molecular weight was 6500.

&Lt; Synthesis Example 20: Synthesis of Specific Resin T) >

PGMEA (12.4 g) was placed in a three-necked flask, and the temperature was raised to 70 占 폚 in a nitrogen atmosphere. MAHA (0.603 g), HEMA (1.821 g), MATHF (4.373 g), OXE-30 (3.868 g) and V-65 (1.217 g, 7 mol% based on monomer) were dissolved in PGMEA (12.4 g) And dropped for 2 hours. After completion of dropwise addition, stirring was performed for 4 hours to terminate the reaction. Thus, a specific resin T was obtained (acid value = 36.82, I / O value = 0.686). The weight average molecular weight was 6500.

Synthesis Example 21: Synthesis of Specific Resin U)

PGMEA (12.2 g) was placed in a three-necked flask, and the temperature was raised to 70 占 폚 in a nitrogen atmosphere. MAHA (0.603 g), HEMA (2.277 g), MATHF (4.373 g), OXE-30 (3.224 g) and V-65 (1.217 g, 7 mol% based on monomer) were dissolved in PGMEA (12.2 g) And dropped for 2 hours. After completion of dropwise addition, stirring was performed for 4 hours to terminate the reaction. Thereby, a specific resin U was obtained (acid value = 37.49, I / O value = 0.730). The weight average molecular weight was 6500.

&Lt; Synthesis Example 22: Synthesis of B5 >

1-1. Synthesis of Synthetic Intermediate B5-A

31.3 g (manufactured by Tokyo Chemical Industry Co., Ltd.) of 2-aminobenzenethiol was dissolved in 100 mL of toluene (manufactured by Wako Pure Chemical Industries, Ltd.) at room temperature (25 占 폚). Then, 40.6 g of phenylacetyl chloride (manufactured by TOKYO KASEI KOGYO CO., LTD.) Was added dropwise to the obtained solution, and the mixture was stirred at room temperature for 1 hour and then at 100 DEG C for 2 hours. 500 ml of water was added to the obtained reaction solution to dissolve the precipitated salt, toluene oil was extracted and the extract was concentrated with a rotary evaporator to obtain a synthetic intermediate B5-A.

1-2. Synthesis of B5

2.25 g of the thus-obtained synthetic intermediate B5-A was mixed with 10 mL of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) and immersed in an ice bath to cool the reaction solution to 5 占 폚 or less. Next, 4.37 g of tetramethylammonium hydroxide (25% methanol solution, manufactured by Alfa Acer) was added dropwise to the reaction solution, and the mixture was reacted with stirring for 0.5 hour in an ice bath. Further, 7.03 g of isopentyl nitrite was added dropwise while keeping the internal temperature at 20 캜 or lower. After completion of dropwise addition, the reaction solution was heated to room temperature and stirred for 1 hour.

Subsequently, the reaction solution was cooled to 5 캜 or lower, p-toluenesulfonyl chloride (1.9 g, manufactured by Tokyo Chemical Industry Co., Ltd.) was added thereto, and the mixture was stirred for 1 hour while maintaining the temperature at 10 캜 or lower. Then, 80 mL of water was added, and the mixture was stirred at 0 ° C for 1 hour. The resultant precipitate was filtered, and 60 mL of isopropyl alcohol (IPA) was added. The mixture was heated to 50 占 폚, stirred for 1 hour, filtered (hot) and dried to obtain 1.8 g of (B5: the following structure).

The obtained ¹ H-NMR spectrum of the obtained B5 (300 MHz, DMSO ((D ₃ C) ₂ S = O)) was found to be δ = 8.2-8.17 (m, 1H), 8.03-8.00 (m, 2H), 7.6-7.45 (m, 9H), 2.45 (s, 3H).

From the ¹ H-NMR measurement results, it is estimated that the obtained B5 is a single geometric isomer.

&Lt; Synthesis Example 23: Synthesis of B6 >

Aluminum chloride (10.6 g) and 2-chloropropionyl chloride (10.1 g) were added to a suspension of 2-naphthol (10 g) and chlorobenzene (30 mL), and the mixture was heated to 40 캜 for reaction for 2 hours. 4N HCl aqueous solution (60 mL) was added dropwise to the reaction solution under ice-cooling, and ethyl acetate (50 mL) was added to separate the layers. Potassium carbonate (19.2 g) was added to the organic layer, and the mixture was reacted at 40 占 폚 for 1 hour. 2N HCl aqueous solution (60 mL) was added thereto and the mixture was separated. The organic layer was concentrated, and the crystals were reslurried with diisopropyl ether , Filtered and dried to obtain a ketone compound (6.5 g).

Acetic acid (7.3 g) and a 50% aqueous solution of hydroxyamine (8.0 g) were added to the resulting suspension of the ketone compound (3.0 g) and methanol (18 mL), and the mixture was heated under reflux for 10 hours. After cooling, water (50 mL) was added, and the precipitated crystals were filtered, washed with cold methanol, and dried to obtain an oxime compound (2.4 g).

The obtained oxime compound (1.8 g) was dissolved in acetone (20 mL), triethylamine (1.5 g) and p-toluenesulfonyl chloride (2.4 g) were added under ice-cooling, and the mixture was heated to room temperature and reacted for 1 hour. Water (50 mL) was added to the reaction solution, and the precipitated crystals were filtered and then slurry was rinsed with methanol (20 mL), followed by filtration and drying to obtain 2.3 g of B6 (the following structure).

In addition, ¹ H-NMR spectrum of B6 (300MHz, CDCl ₃₎ is, δ = 8.3 (d, 1H ), 8.0 (d, 2H), 7.9 (d, 1H), 7.8 (d, 1H), 7.6 (dd 1H), 7.4 (dd, 1H), 7.3 (d, 2H), 7.1 (d, 1H), 5.6 (q,

&Lt; Synthesis Example 24: Synthesis of B7 >

B7 (the following structure) was synthesized in the same manner as B6 except that benzenesulfonyl chloride was used instead of p-toluenesulfonyl chloride in the synthesis of B6.

In addition, ¹ H-NMR spectrum of the B7 (300MHz, CDCl ₃₎ is, δ = 8.3 (d, 1H ), 8.1 (d, 2H), 7.9 (d, 1H), 7.8 (d, 1H), 7.7-7.5 (m, 4H), 7.4 (dd, 1H), 7.1 (d, 1H), 5.6 (q,

&Lt; Synthesis Example 25: Synthesis of B8 >

2-Naphthol (20 g) was dissolved in N, N-dimethylacetamide (150 mL), potassium carbonate (28.7 g) and ethyl 2-bromooxinate (52.2 g) were added and reacted at 100 ° C for 2 hours. 48% aqueous sodium hydroxide solution (23 g), ethanol (50 mL) and water (50 mL) were added to the reaction mixture, and water (300 mL) and ethyl acetate (200 mL) . The reaction solution was poured into 1N HCl aqueous solution (500 mL), and the precipitated crystals were filtered and washed with water to obtain a crude carboxylic acid. Then, 30 g of polyphosphoric acid was added and reacted at 170 DEG C for 30 minutes. The reaction solution was poured into water (300 mL), and ethyl acetate (300 mL) was added and the solution was separated. The organic layer was concentrated and purified by silica gel column chromatography to obtain a ketone compound (10 g).

Sodium acetate (30.6 g), hydrochloric acid hydroxyamine (25.9 g) and magnesium sulfate (4.5 g) were added to the resulting suspension of the ketone compound (10.0 g) and methanol (100 mL) and the mixture was refluxed for 24 hours. After cooling, water (150 mL) and ethyl acetate (150 mL) were added and the solution was separated. The organic layer was separated into four portions of 80 mL of water, concentrated, and then purified by silica gel column chromatography to obtain an oxime compound (5.8 g).

The resulting oxime (3.1 g) was sulfonated as in B6 to obtain 3.2 g of B8 (the following structure).

In addition, ¹ H-NMR spectrum of B8 (300MHz, CDCl ₃₎ is, δ = 8.3 (d, 1H ), 8.0 (d, 2H), 7.9 (d, 1H), 7.8 (d, 1H), 7.6 (dd , 7.5 (dd, 1H), 7.3 (d, 2H), 7.1 (d, 1H), 5.6 (dd, 1H), 1.4-1.2 (m, 8H), 0.8 (t, 3H).

&Lt; Comparative Synthesis Example 1: Synthesis of Comparative Resin R1 >

HS-DEM (31.5 g) was placed in a three-necked flask, and the temperature was raised to 70 占 폚 in a nitrogen atmosphere. To this solution was added HS-EDM (31.5 g), MAA (1.72 g), EtMA (9.13 g), OXE-30 (10.05 g), HEMA (5.20 g), V- And the solution was added dropwise over 2 hours. After completion of dropwise addition, stirring was performed for 4 hours to terminate the reaction. Thus, a comparative resin R1 was obtained (acid value = 41.39, I / O value = 0.679). The weight average molecular weight was 6600.

&Lt; Comparative Synthesis Example 2: Synthesis of comparative resin R2 >

HS-DEM (34.5 g) was placed in a three-necked flask, and the temperature was raised to 70 占 폚 in a nitrogen atmosphere. To this solution was added MAA (1.72 g), HMA (10.22 g), MAEVE (12.65 g), HEMA (5.20 g) and V-65 (3.47 g, 7 mol% based on monomer) dissolved in 34.5 g of HS- And dropped for 2 hours. After completion of dropwise addition, stirring was performed for 4 hours to terminate the reaction. Thereby, comparative resin R2 was obtained (acid value = 37.60, I / O value = 0.622). The weight average molecular weight was 7100.

&Lt; Comparative Synthesis Example 3: Synthesis of comparative resin R3 >

The resin described as Synthesis Example 2 was synthesized in the specification of Japanese Patent No. 4207604 to obtain a comparative resin R3 (acid value = 0, I / O value = 0.653). The weight average molecular weight was 8,000.

&Lt; Comparative Synthesis Example 4: Synthesis of comparative resin R4 >

A resin described as Synthesis Example A-7 was synthesized in Japanese Patent Laid-Open Publication No. 2009-986216 to give a comparative resin R4 (acid value = 33.89, I / O value = 0.542). The weight average molecular weight was 6500.

&Lt; Comparative Synthesis Example 5: Synthesis of comparative resin R5 >

HS-DEM (32.5 g) was placed in a three-necked flask, and the temperature was raised to 70 캜 under a nitrogen atmosphere. To this solution, MAA (5.16 g), MAEVE (12.65 g), OXE-30 (10.21 g) and V-65 (3.47 g, 7 mol% based on monomer) were dissolved in HS- EDM (32.5 g) I dropped it. After completion of dropwise addition, stirring was performed for 4 hours to terminate the reaction. As a result, a comparative resin R5 was obtained (acid value = 116.59, I / O value = 0.682). The weight average molecular weight was 6700.

&Lt; Comparative Synthesis Example 6: Synthesis of comparative resin R6 >

The resin described as Synthesis Example 3 was synthesized in the specification of Japanese Patent No. 3693199 to obtain a comparative resin R6 (acid value = 130.35, I / O value = 0.643). The weight average molecular weight was 8,000.

&Lt; Comparative Synthesis Example 7: Synthesis of comparative resin R7 >

HS-DEM (36.0 g) was placed in a three-necked flask, and the temperature was raised to 70 占 폚 in a nitrogen atmosphere. (3.44 g), MAEVE (12.66 g), OXE-30 (14.74 g) and V-65 (3.47 g, 7 mol% based on monomer) were dissolved in 36.0 g of HS-EDM, I dropped it. After completion of dropwise addition, stirring was performed for 4 hours to terminate the reaction. Thereby, comparative resin R7 was obtained (acid value = 72.78, I / O value = 0.588). The weight average molecular weight was 6800.

&Lt; Comparative Synthesis Example 8: Synthesis of comparative resin R8 >

HS-DEM (34.0 g) was placed in a three-neck flask, and the temperature was raised to 70 占 폚 in a nitrogen atmosphere. To this solution was dissolved MA-H (5.34 g), MAEVE (0.32 g), OXE-30 (25.06 g) and V-65 (3.47 g, 7 mol% based on monomer) in HS- EDM (34.0 g) I dropped it. After completion of dropwise addition, stirring was performed for 4 hours to terminate the reaction. Thereby, comparative resin R8 was obtained (acid value = 113.28, I / O value = 0.626). The weight average molecular weight was 7400.

&Lt; Comparative Synthesis Example 9: Synthesis of comparative resin R9 >

HS-DEM (32.0 g) was placed in a three-necked flask, and the temperature was raised to 70 캜 in a nitrogen atmosphere. To this solution was added HS-EDM (32.0 g), MAA (5.16 g), HEMA (4.69 g), MAEVE (7.90 g), OXE-30 (9.95 g), V- And the solution was added dropwise over 2 hours. After completion of dropwise addition, stirring was performed for 4 hours to terminate the reaction. As a result, a comparative resin R9 was obtained (acid value = 121.50, I / O value = 0.827). The weight average molecular weight was 7200.

&Lt; Comparative Synthesis Example 10: Synthesis of comparative resin R10 >

HS-DEM (33.0 g) was placed in a three-necked flask, and the temperature was raised to 70 占 폚 in a nitrogen atmosphere. To this solution was added HS-EDM (33.0 g), MAA (3.79 g), HEMA (7.80 g), MAEVE (5.69 g), OXE-30 (11.05 g), V- And the solution was added dropwise over 2 hours. After completion of dropwise addition, stirring was performed for 4 hours to terminate the reaction. As a result, a binder R10 was obtained (acid value = 87.10, I / O value = 0.838). The weight average molecular weight was 6600.

&Lt; Comparative Synthesis Example 11: Synthesis of comparative resin R11 >

HS-DEM (33.5 g) was put in a three-necked flask, and the temperature was raised to 70 占 폚 in a nitrogen atmosphere. To this solution was added HS-EDM (33.5 g), MAA (1.72 g), MAEVE (9.49 g), OXE-30 (7.37 g), HEMA (10.41 g), V- And the solution was added dropwise over 2 hours. After completion of dropwise addition, stirring was performed for 4 hours to terminate the reaction. Thereby, comparative resin R11 was obtained (acid value = 38.71, I / O value = 0.826). The weight average molecular weight was 7300.

[Examples 1 to 33, Comparative Examples 1 to 11]

The components shown in Table 1 or Table 2 were mixed to obtain a homogeneous solution and then filtered using a polytetrafluoroethylene filter having a pore size of 0.2 mu m to obtain a solution of each of Examples 1 to 33 and Comparative Examples 1 to 11 photosensitive resin compositions were respectively prepared. The amount of the specific resin or the comparative resin shown in Table 1 or Table 2 is the mass part of the resin solution obtained by synthesis of each resin.

[Table 1]

[Table 2]

The abbreviations in Table 1 or Table 2 are as follows.

B1: CGI1397 (the following structure, manufactured by Chiba Japan Co., Ltd.)

B2: CGI1325 (the following structure, manufactured by Chiba Japan Co., Ltd.)

B3: PAI-1001 (manufactured by Hideki Corporation, Midori Kagaku Co., Ltd.)

B4: PAI-1003 (manufactured by Hideki Corporation, Midori Kagaku Co., Ltd.)

B5: benzothiazole acid generator (the following structure, synthesized by Synthesis Example 22)

B6: Naphthofuluanone oxime acid generating agent 1 (the following structure, synthesized by Synthesis Example 23)

B7: Naphthofuluanone oxime acid generator 2 (the following structure, synthesized by Synthesis Example 24 above)

B8: Naphthofuluanone oxime acid generator 3 (the following structure, synthesized by Synthesis Example 25 above)

C1: Propylene glycol monomethyl ether acetate

C2: diethylene glycol ethyl methyl ether

D1: Adecastab AO-60 (the following structure, manufactured by ADEKA Corporation)

E1: JER-157S70 (polyfunctional novolac epoxy resin (epoxy equivalents: 200 to 220 g / eq), Japan Epoxy Resin Co., Ltd.)

F1: KBM-403 (manufactured by Shinetsu Kagaku Kogyo Co., Ltd.)

G1: 4-Dimethylaminopyridine

G2: 1,5-Diazabicyclo [4.3.0] -5-nonene

H1: Megapack R-08 (a nonionic surfactant containing a perfluoroalkyl group, manufactured by DIC Corporation)

H2: a perfluoroalkyl group-containing nonionic surfactant represented by the following structural formula (W-3)

I1: DBA (9,10-dibutoxyanthracene, the following structure, manufactured by Kawasaki Chemical Industry Co., Ltd.)

I2: DEA (9,10-diethoxyanthracene, the following structure, manufactured by Kawasaki Chemical Industry Co., Ltd.)

B5, B6, and B8, Ts represents a tosyl group.

(2) Evaluation of sensitivity

The photosensitive resin composition of each of the Examples and Comparative Examples was coated with a slit on a silicon wafer having a silicon oxide film and then prebaked on a hot plate at 95 캜 for 90 seconds to form a coating film having a thickness of 3 탆.

Next, using an i-line stepper (FPA-3000i5 + manufactured by Canon Inc.), exposure was performed through a predetermined mask. After exposure, the resist film was developed with a 0.4% tetramethylammonium hydroxide aqueous solution at 23 캜 for 80 seconds by a liquid method, and then rinsed with ultrapure water for 1 minute. By these operations, the optimum exposure amount at the time of resolving the line-and-space of 10 mu m at a ratio of 1: 1 was taken as the sensitivity. The sensitivity can be said to be high sensitivity when the exposure amount is lower than 100 mJ / cm ² .

(3) Evaluation of the residual film ratio of the unexposed portion

The film thickness of the unexposed portion after development of the formed coating film as in the evaluation of the sensitivity was measured with a contact type film thickness meter and the ratio of the remaining film thickness to the initial measured film thickness was evaluated as the remaining film ratio. That is, "unexposed portion residual film ratio = film thickness after development (unexposed portion) / film thickness before development (unexposed portion) x 100". It can be said that the residual film ratio of the unexposed portion is 85% or more in a practical range, which is good.

(4) Evaluation of transparency

A photosensitive resin composition solution was slit coated on a glass substrate &quot; Corning 1737 (manufactured by Corning) &quot;, and then prebaked on a hot plate at 95 캜 for 90 seconds to form a coating film having a thickness of 3 탆. The obtained coating film was exposed with a PLA-501F exposure apparatus (ultra-high pressure mercury lamp) manufactured by Canon Inc. so as to have a cumulative dose of 200 mJ / cm ² (light intensity: 20 mW / cm ² ) And heated for a time to obtain a cured film. The obtained cured film was further heated in an oven at 230 캜 for 2 hours, and then the light transmittance was measured at a wavelength in the range of 400 to 800 nm using a spectrophotometer "150-20 type double beam (manufactured by Hitachi Seisakusho Co., Ltd.)" . The evaluation of the transmittance at 400 nm at that time was taken as the evaluation of transparency. If this value is 90% or more, it can be said that heat-resistant transparency is good.

(5) Evaluation of relative dielectric constant

A photosensitive resin composition solution was slit coated on a bare wafer (N type low resistance) (manufactured by SUMCO), and then baked on a hot plate at 90 DEG C for 2 minutes to form a photosensitive resin composition layer having a film thickness of 3.0 mu m . The obtained photosensitive resin composition was exposed to a cumulative dose of 300 mJ / cm ² (illuminance: 20 mW / cm ² ) with a PLA-501F exposure apparatus (ultra-high pressure mercury lamp) manufactured by Canon Inc., By heating for a time, a cured film was obtained.

The relative dielectric constant of this cured film was measured at a measurement frequency of 1 MHz using CVmap92A (manufactured by Four Dimensions Inc.). The results are shown in Table 2. When this value is 3.9 or less, the relative dielectric constant of the cured film is considered to be good.

(6) Evaluation of residues

Each of the photosensitive resin composition solutions was coated with a slit as in the evaluation of sensitivity, and then pre-baked on a hot plate at 95 캜 for 90 seconds to form a coating film having a thickness of 3 탆.

The resulting coating film was subjected to pattern exposure at an optimum exposure amount in a circular pattern through a mask for forming a contact hole of 10 mu m and rinsed after development as in the evaluation of sensitivity. With respect to the residue of the end portion of the obtained circular pattern (cured film), the distance from the place where the cured film was formed to the place where the film completely disappeared was observed using an optical microscope. The evaluation criteria are as follows.

A: less than 1.0 탆

B: 1.0 占 퐉 or more to less than 3.0 占 퐉

C: 3.0 탆 or more

(7) Evaluation of surface roughness

A cured film was formed as in the evaluation of heat resistance transparency.

For the obtained post-baked cured film, the Ra of the surface of the cured film was measured using a contact film thickness meter (a contact-type surface roughness meter P10 manufactured by Tencor Co., Ltd.) and evaluated according to the following evaluation criteria.

A: less than 5.0 nm

B: 5.0 nm or more and less than 10 nm

C: 10 nm or more

The evaluation results are summarized in Table 3. In Table 3, "-" in a part of the comparative example indicates that the residual film ratio of the unexposed portion was small and the pattern could not be formed.

[Table 3]

The results are shown in Table 3. In Table 3, the photosensitive resin compositions of the respective Examples containing specific resins showed high sensitivity in comparison with the photosensitive resin compositions of the respective comparative examples, the occurrence of residue was suppressed, the surface roughness of the cured film formed did not occur , Furthermore, transparency and heat resistance transparency are excellent, and good results are obtained in the evaluation of the relative dielectric constant.

[Example 34]

The photosensitive resin composition solution used in Example 4 was slit coated on a silicon wafer having a silicon oxide film and then prebaked on a hot plate at 95 캜 for 90 seconds to form a coating film having a thickness of 3 탆.

Next, after an interval of 150㎛ from the coating film, by setting a predetermined photomask, the laser having a wavelength of 355nm, was irradiated with the exposure dose 15mJ / cm ^2. The laser device used was "AEGIS" (wavelength 355 nm, pulse width 6 nsec) manufactured by Kabushiki Kaisha V Technology Co., Ltd., and the amount of exposure was measured using "PE10B-V2" manufactured by OPHIR. After the exposure, the resist film was developed with a 0.4% tetramethylammonium hydroxide aqueous solution at 23 캜 for 80 seconds by a liquid method, and then rinsed with ultrapure water for 1 minute. By these operations, a line and space of 10 mu m can be resolved at a ratio of 1: 1.

[Example 35]

An organic EL display device using a thin film transistor (TFT) was produced by the following method (see Fig. 1).

A bottom gate type TFT 1 was formed on a glass substrate 6 and an insulating film 3 made of Si ₃ N ₄ was formed so as to cover the TFT 1. Next, a contact hole (not shown) is formed in the insulating film 3, and a wiring 2 (height 1.0 mu m) connected to the TFT 1 through the contact hole is formed on the insulating film 3 did. The wiring 2 is for connecting the organic EL element formed between the TFTs 1 or a subsequent step to the TFT 1. [

The planarization layer 4 was formed on the insulating film 3 so as to fill the irregularities formed by the wirings 2 in order to planarize the irregularities due to the formation of the wirings 2. The planarizing film 4 on the insulating film 3 was formed by spin-coating the photosensitive resin composition of Example 12 on a substrate, pre-baking it on a hot plate (90 占 폚 for 2 minutes) (365 nm) was irradiated with 15 mJ / cm ² (illumination: 20 mW / cm ² ), and then developed with an aqueous alkali solution to form a pattern, and heat treatment was performed at 230 ° C. for 60 minutes. The coating properties upon application of the photosensitive resin composition were good, and no wrinkles or cracks were observed in the cured film obtained after exposure, development and firing. The average step of the wiring 2 was 500 nm, and the thickness of the planarization film 4 was 2,000 nm.

Next, a bottom-emission type organic EL device was formed on the obtained planarization film (4). First, a first electrode 5 made of ITO was formed on the flattening film 4 by being connected to the wiring 2 via the contact hole 7. Thereafter, the resist was applied, pre-baked, exposed through a mask of a desired pattern, and developed. Using this resist pattern as a mask, patterning was carried out by wet etching using ITO etchant. Thereafter, the resist pattern was peeled off using a resist stripping solution (mixture of monoethanolamine and dimethyl sulfoxide (DMSO)). The first electrode 5 thus obtained corresponds to the anode of the organic EL element.

Next, an insulating film 8 having a shape covering the periphery of the first electrode 5 was formed. The insulating film 8 was formed using the photosensitive resin composition of Example 7 by the same method as described above. By providing the insulating film 8, it is possible to prevent a short circuit between the first electrode 5 and the second electrode formed in a subsequent step.

Further, a hole transporting layer, an organic light emitting layer, and an electron transporting layer were sequentially deposited by evaporation through a desired pattern mask in a vacuum vapor deposition apparatus. Then, a second electrode made of Al was formed on the entire upper surface of the substrate. The obtained substrate was removed from the evaporator, and sealed by bonding using a sealing glass plate and an ultraviolet curable epoxy resin.

As described above, an active matrix type organic EL display device in which TFTs 1 for driving the organic EL elements are connected to each organic EL element was obtained. When a voltage was applied through the driving circuit, it was found that the organic EL display device exhibited good display characteristics and was highly reliable.

[Example 36]

In the active matrix type liquid crystal display device shown in Figs. 1 and 2 of Japanese Patent No. 3321003, a cured film 17 as an interlayer insulating film was formed as follows to obtain a liquid crystal display device of Example 36. [

That is, using the photosensitive resin composition of Example 12, a cured film 17 was formed as an interlayer insulating film in the same manner as in the method of forming the planarization film 4 of the organic EL display device in Example 35. [

When the driving voltage was applied to the obtained liquid crystal display device, it was found that the liquid crystal display device exhibited good display characteristics and was highly reliable.

1: TFT (thin film transistor)
2: Wiring
3: Insulating film
4: Planarizing film
5: First electrode
6: glass substrate
7: Contact hole
8: Insulating film
10: Liquid crystal display
12: Backlight unit
14, 15: glass substrate
16: TFT
17:
18: Contact hole
19: ITO transparent electrode
20: liquid crystal
22: Color filter

Claims (21)

(I) obtained by dividing an inorganic value (I) based on an organic conceptual diagram by an organic value (O), wherein the resin (A) contains a resin (A) and a radiation-sensitive acid generator / O value of not less than 0.6 and not more than 0.8, an acid value of not less than 5 mgKOH / g and not more than 110 mgKOH / g, and a resin having an acid group, an acid group and a crosslinkable group protected with an acid decomposable group. The method according to claim 1,
Wherein the resin (A) is a resin having an I / O value of 0.6 or more and 0.8 or less and an acid value of 20 mgKOH / g or more and 70 mgKOH / g or less. The method according to claim 1,
Wherein the acid group is a carboxyl group or a phenolic hydroxyl group. The method according to claim 1,
Wherein the acid group protected by the acid-decomposable group is a group which generates a carboxyl group or a phenolic hydroxyl group by the action of an acid. The method according to claim 1,
Wherein the acid group is a carboxyl group and the acid group protected by the acid decomposable group is a group which generates a carboxyl group by the action of an acid. The method according to claim 1,
Wherein the crosslinking group is an epoxy group or an oxetanyl group. The method according to claim 1,
Wherein the resin (A) is a copolymer containing a structural unit derived from a radically polymerizable compound containing an acid group protected by an acid-decomposable group, a radical polymerizable compound containing an unsaturated carboxylic acid and a radical polymerizable compound containing an epoxy group or an oxetanyl group, Resin composition. 8. The method of claim 7,
Wherein the radically polymerizable compound containing an epoxy group or an oxetanyl group is a radically polymerizable compound containing an oxetanyl group. 8. The method of claim 7,
Wherein the resin (A) is a copolymer containing at least one structural unit selected from the group consisting of a hydroxyl group-containing unsaturated carboxylic acid ester, an alicyclic structure-containing unsaturated carboxylic acid ester, styrene and N-substituted maleimide, Composition. The method according to claim 1,
Wherein the radiation-sensitive acid generator (B) is a compound having an oxime sulfonate group. The method according to claim 1,
Wherein the radiation-sensitive acid generator (B) is a compound represented by the following general formula (OS-3).

(In the general formula (OS-3), R ¹ represents an alkyl group, an aryl group or a heteroaryl group, and the plurality of R ^{2 s} present each independently represent a hydrogen atom, an alkyl group, an aryl group or a halogen atom, R ⁶ , which may be present in plural numbers, 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). The method according to claim 1,
(A) is contained in an amount of 60% by mass to 95% by mass relative to the total solid content of the positive photosensitive resin composition and 0.1% by mass to 10% by mass of the radiation-sensitive acid generator (B) By weight based on the total weight of the positive photosensitive resin composition. The method according to claim 1,
Further, a positive photosensitive resin composition containing a crosslinking agent. 14. The method of claim 13,
Wherein the resin (A) is contained in an amount of 40% by mass to 70% by mass relative to the total solid content of the positive photosensitive resin composition and the radiation-sensitive acid generator (B) is contained in a range of 0.1% by mass to 10% By weight of the crosslinking agent, and the crosslinking agent is contained in an amount of 3% by mass to 40% by mass. A cured film obtained by curing a positive photosensitive resin composition according to claim 1 by applying at least one of light and heat. (1) a coating step of applying the positive-working photosensitive resin composition according to any one of claims 1 to 14 on a substrate,
(2) a solvent removing step of removing the solvent from the applied positive photosensitive resin composition,
(3) an exposure step of exposing the positive photosensitive resin composition from which the solvent has been removed to active radiation,
(4) a developing step of developing the exposed positive photosensitive resin composition with an aqueous developing solution, and
(5) a post-baking step of thermally curing the developed positive photosensitive resin composition
To form a cured film. 17. The method of claim 16,
Wherein the developing step is performed after the exposure in the exposure step without performing the heat treatment. A cured film formed by the method for forming a cured film according to claim 16. 16. The method of claim 15,
A cured film which is an interlayer insulating film. A liquid crystal display device comprising the cured film according to claim 15. An organic EL display device comprising the cured film according to claim 15.

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