KR20150027201A - Photosensitive resin composition, cured product, method for producing cured product, method for producing resin pattern, cured film, liquid crystal display device, organic el display device, and touch panel display device - Google Patents

Abstract

(1) (a1) 산기가 산 분해성기로 보호된 기를 갖는 구성 단위, 및 (a2) 가교성기를 갖는 구성 단위를 갖는 중합체
(2) (a1) 산기가 산 분해성기로 보호된 기를 갖는 구성 단위를 갖는 중합체, 및 (a2) 가교성기를 갖는 구성 단위를 갖는 중합체It is an object of the present invention to provide a photosensitive resin composition having high refractive index and excellent transparency.
In the photosensitive resin composition of the present invention,
(Component A) A polymer component comprising a polymer satisfying at least one of (1) and (2)
(Component S) A dispersant represented by the formula (S) and having at least one acid group,
(Component B) Photoacid generators,
(Component C) metal oxide particles, and
(Component D) solvent.

(1) A resin composition comprising (a1) a structural unit having an acid group protected with an acid-decomposable group, and (a2) a polymer having a structural unit having a crosslinkable group
(2) a polymer having (a1) a structural unit having a group protected with an acid-decomposable group, and (a2) a polymer having a structural unit having a crosslinkable group

Description

TECHNICAL FIELD [0001] The present invention relates to a photosensitive resin composition, a cured product and a method for producing the same, a method for producing a resin pattern, a cured film, a liquid crystal display, an organic EL display, and a touch panel display. RESIN PATTERN, CURED FILM, LIQUID CRYSTAL DISPLAY DEVICE, ORGANIC EL DISPLAY DEVICE, AND TOUCH PANEL DISPLAY DEVICE}

The present invention relates to a photosensitive resin composition (hereinafter sometimes simply referred to as " composition of the present invention "). The present invention also relates to a cured product obtained by curing the photosensitive resin composition, a method for producing the same, a resin pattern production method using the photosensitive resin composition, a cured film obtained by curing the photosensitive composition, and various image display devices using the cured film .

More particularly, the present invention relates to a planarizing film for electronic components such as a liquid crystal display device, an organic EL display device, a touch panel display device, an integrated circuit device, and a solid-state imaging device, a photosensitive resin composition suitable for forming a protective film or an interlayer insulating film, ≪ / RTI >

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

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

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

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

An object of the present invention is to provide a photosensitive resin composition having high refractive index and excellent transparency.

The above problem of the present invention is solved by the means described in the following <1>, <8> - <11> or <13> - <15>. Are described below together with <2> to <7> and <12> which are preferred embodiments.

(1) a polymer component comprising (a1) a structural unit having an acid group protected with an acid-decomposable group and (a2) a structural unit having an acid group protected with an acid-decomposable group, and (a2) (2) a polymer having (a1) a constituent unit having a group protected with an acid-decomposable group and (a2) a constituent unit having a crosslinkable group, (Component S) a polymer having a constituent unit , A dispersant represented by the following formula (S) and having at least one acid group, (Component B) a photo acid generator, (Component C) metal oxide particles, and (Component D)

(In the formula (S), R ³ represents a linking group of (m + n), R ⁴ and R ⁵ each independently represent a single bond or a divalent linking group, A ² represents an organic pigment structure, , A group having a basic nitrogen atom, a urea group, a urethane group, a group having a radial oxygen atom, an alkoxysilyl group, a phenol group, an alkyl group, an aryl group, a group having an alkyleneoxy group, an imide group, an alkyloxycarbonyl group, A monovalent organic group containing at least one partial structure selected from the group consisting of an aminocarbonyl group, a carboxylate group, a sulfonamide group, an epoxy group, an isocyanate group and a hydroxyl group, n A ² and R ⁴ may be the same or different, m represents 0 to 8, n represents 2 to 9, m + n represents 3 to 10, P ² represents a polymer skeleton, and m P ² and R ⁵ may be the same or different)

<2> The photosensitive resin composition according to <1>, wherein the component C is titanium oxide particles or zirconium oxide particles,

<3> The photosensitive resin composition according to <1> or <2>, wherein the A ² is a monovalent organic group containing at least one acid group,

<4> The photosensitive resin composition according to any one of <1> to <3>, wherein the P ² is an acrylic resin skeleton,

<5> The photosensitive resin composition according to any one of <1> to <4>, wherein the component A comprises a polymer satisfying the above-mentioned (1)

<6> (Component E) The photosensitive resin composition according to any one of <1> to <5>, further comprising a crosslinking agent.

<7> (Component F) The photosensitive resin composition according to any one of <1> to <6>, further comprising an antioxidant,

<8> A process for producing a cured product comprising at least the steps (a) to (c)

(a) a coating step of applying the photosensitive resin composition described in any one of < 1 > to < 7 >

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

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

<9> A resin pattern manufacturing method comprising at least steps (1) to (5) in this order,

(1) a coating step of applying the photosensitive resin composition described in any one of < 1 > to < 7 &

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

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

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

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

&Lt; 10 > A cured product according to the above <8>, or a cured product obtained by the resin pattern production method described in <9>

<11> A cured film obtained by curing the photosensitive resin composition according to any one of <1> to <7>

<12> The cured film according to <11> which is an interlayer insulating film,

<13> A liquid crystal display device having the cured film according to <11> or <12>

<14> An organic EL display device having the cured film according to <11> or <12>

<15> A touch panel display device having a cured film according to <11> or <12>.

(Effects of the Invention)

According to the present invention, a photosensitive resin composition having high refractive index and excellent transparency can be provided.

Fig. 1 shows a configuration diagram of an example of a liquid crystal display device. Sectional view of an active matrix substrate in a liquid crystal display device and has a cured film 17 as an interlayer insulating film.
2 shows a configuration diagram of an example of the organic EL display device. Sectional schematic view of a substrate in a bottom emission type organic EL display device and has a planarization film 4. [
3 is a cross-sectional view showing the configuration of the capacitance type input device.
4 is an explanatory diagram showing an example of a front surface plate.
5 is an explanatory view showing an example of the first transparent electrode pattern and the second transparent electrode pattern.

Hereinafter, the contents of the present invention will be described in detail. The following description of the constituent elements described below may be made on the basis of exemplary embodiments of the present invention, but the present invention is not limited to such embodiments.

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

In the present invention, the "polymer component comprising a polymer satisfying at least one of (Component A) and (2) below" may be simply referred to as "Component A" or the like, and "(a1) And a structural unit having a group protected by a decomposable group &quot; may be simply referred to as &quot; structural unit (a1) &quot;.

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

Further, the combination of the preferable forms in the present invention is more preferable.

(Photosensitive resin composition)

(A) a polymer component comprising a polymer satisfying at least one of the following (1) and (2); (Component S) a polymer component comprising a polymer satisfying at least one of the following formulas (Component B) a photoacid generator, (Component C) metal oxide particles, and (Component D) a solvent, which is represented by the following formula (1)

(1) a polymer having (a1) a structural unit having a group protected by an acid-decomposable group and (a2) a structural unit having a crosslinkable group

(2) a polymer having (a1) a structural unit having a group protected with an acid-decomposable group, and (a2) a polymer having a structural unit having a crosslinkable group

(In the formula (S), R ³ represents a linking group of (m + n), R ⁴ and R ⁵ each independently represent a single bond or a divalent linking group, A ² represents an organic pigment structure, , A group having a basic nitrogen atom, a urea group, a urethane group, a group having a radial oxygen atom, an alkoxysilyl group, a phenol group, an alkyl group, an aryl group, a group having an alkyleneoxy group, an imide group, an alkyloxycarbonyl group, A monovalent organic group containing at least one partial structure selected from the group consisting of an aminocarbonyl group, a carboxylate group, a sulfonamide group, an epoxy group, an isocyanate group and a hydroxyl group, n A ² and R ⁴ may be the same or different, m represents 0 to 8, n represents 2 to 9, m + n represents 3 to 10, P ² represents a polymer skeleton (also referred to as "polymer chain"), and m P ² and R ⁵ are the same Or may be different]

The photosensitive resin composition of the present invention can be preferably used as a positive resist composition.

The photosensitive resin composition of the present invention is preferably a resin composition having properties of being cured by heat.

Further, the photosensitive resin composition of the present invention is preferably a positive photosensitive resin composition, more preferably a positive-working photosensitive resin composition (chemically amplified positive photosensitive resin composition).

The photosensitive resin composition of the present invention preferably does not contain a 1,2-quinonediazide compound as a photoacid generator which is sensitive to an actinic ray. The 1,2-quinonediazide compound produces a carboxyl group by a sequential photochemical reaction, but its quantum yield is not more than 1.

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

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

Generally, when a chemically amplified positive photosensitive resin composition is exposed to light, the releasing group of the polymer contained in the polymer is dissolved by the action of the photoacid generator to dissolve in the developer, and an unexposed portion is formed as a pattern.

When a resin composition containing a polymer containing inorganic particles, a dispersant and a releasing agent and a crosslinking group is used as the positive photosensitive resin composition, the dispersibility of the inorganic particles is very important, and if the dispersion is not properly performed, There is a problem that transparency deteriorates when the photosensitive resin composition is finally coated with coarse particles or coarse particles remain without being pulverized. On the other hand, compatibility between the dispersion and the binder in the photosensitive resin composition is also important If the combination is poor, turbidity is generated in the liquid.

As a result of a detailed examination, the inventors of the present invention have found that the use of a photosensitive resin composition containing the components A to D and S improves the dispersibility of the metal oxide particles to improve the compatibility with a binder having a small average particle diameter and no coarse particles A photosensitive resin composition capable of forming a cured product having good high transparency (small haze) and high refractive index can be obtained.

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

(Component A) A polymer composition comprising a polymer satisfying at least one of (1) and (2)

The photosensitive resin composition of the present invention (component A) contains a polymer component comprising a polymer satisfying at least one of the following (1) and (2).

(1) a polymer having (a1) a structural unit having a group protected by an acid-decomposable group and (a2) a structural unit having a crosslinkable group

(2) a polymer having (a1) a structural unit having a group protected with an acid-decomposable group, and (a2) a polymer having a structural unit having a crosslinkable group

The composition of the present invention may further comprise a polymer other than these. Component A in the present invention means, in addition to the above-mentioned (1) and / or (2), other polymers added as required, unless otherwise specified.

From the viewpoints of transparency (haze) after curing and residual film ratio of unexposed portions, the photosensitive resin composition of the present invention preferably contains a component that satisfies the above-mentioned (1) as Component A.

On the other hand, from the viewpoint of freedom of molecular design, the photosensitive resin composition of the present invention preferably contains a component satisfying the above-mentioned (2) as the component A.

(A1) an acrylic resin having a constituent unit having an acid group protected with an acid-decomposable group and / or (a2) an acrylic resin having a constituent unit having a crosslinkable group, It may contain more.

In addition, even when containing a component satisfying the above-mentioned (2), when at least (a1) the acid group has at least a structural unit having a group protected with an acid-decomposable group and (a2) a polymer having a structural unit having a crosslinkable group (1) is contained in the above-mentioned composition.

The component A is preferably an addition polymerization type resin, more preferably a polymer comprising a constituent unit derived from (meth) acrylic acid and / or an ester thereof. Further, it may contain a structural unit other than the structural unit derived from (meth) acrylic acid and / or an ester thereof, for example, a structural unit derived from styrene or a structural unit derived from a vinyl compound.

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

&Lt; Structural unit (a1) >

Component A comprises (a1) a polymer having at least a constituent unit having an acid group protected by an acid-decomposable group. When the component A contains a polymer having the constituent unit (a1), a photosensitive resin composition having extremely high sensitivity can be obtained.

The "group in which the acid group is protected with an acid-decomposable group" in the present invention can be any known acid group and acid decomposable group, and is not particularly limited. Specific examples of the acid group include a carboxyl group and a phenolic hydroxyl group. The acid decomposable group is preferably a group which is relatively easily decomposed by an acid (for example, an ester structure of a group represented by the following formula (a1-10), a tetrahydropyranyl ester group, or a tetrahydrofuranyl ester group (For example, a tertiary alkyl group such as a tert-butyl ester group or a tertiary alkylcarbonate group such as a tert-butylcarbonate group) can be used .

(a1) The constituent unit in which the acid group has a group protected by an acid-decomposable group is a constituent unit in which the carboxyl group is protected by an acid-decomposable group (also referred to as a &quot; constituent unit having a protected carboxyl group protected with an acid-decomposable group &quot;) or a phenolic hydroxyl group Is preferably a structural unit having a protective phenolic hydroxyl group protected by an acid-decomposable group (also referred to as a &quot; structural unit having a protective phenolic hydroxyl group protected with an acid-decomposable group &quot;).

Hereinafter, the structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group and the structural unit (a1-2) having a protected phenolic hydroxyl group protected with an acid-decomposable group will be described in order.

<< (a1-1) Structural unit having a protected carboxyl group protected with an acid-decomposable group >>

The structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group is a structural unit in which the carboxyl group of the structural unit having a carboxyl group has a protected carboxyl group protected by an acid-decomposable group described in detail below.

The structural unit having a carboxyl group which can be used for the structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group is not particularly limited and a known structural unit can be used. (A1-1-1) derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule such as an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid and an unsaturated tricarboxylic acid; , And a structural unit (a1-1-2) having both an ethylenic unsaturated group and an acid anhydride derived structure.

(A1-1-1) a constituent unit derived from an unsaturated carboxylic acid or the like having at least one carboxyl group in the molecule and (a1-1-2) a constituent unit derived from an ethylenic unsaturated group and an acid And structural units having both structures derived from anhydride will be described in order.

<<< (a1-1-1) Constituent derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule >>>

As the constituent unit (a1-1-1) derived from an unsaturated carboxylic acid or the like having at least one carboxyl group in the molecule, the same as exemplified below is used as the unsaturated carboxylic acid used in the present invention. Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid,? -Chloroacrylic acid, cinnamic acid, 2- (meth) acryloyloxyethylsuccinic acid, 2- Ethylhexahydrophthalic acid, 2- (meth) acryloyloxyethylphthalic acid, and the like. Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid. The unsaturated polycarboxylic acid used for obtaining the constituent unit having a carboxyl group may be an acid anhydride thereof. Specific examples thereof include maleic anhydride, itaconic anhydride, and citraconic anhydride. The unsaturated polycarboxylic acid may be a mono (2-methacryloyloxyalkyl) ester of a polycarboxylic acid, for example, mono (2-acryloyloxyethyl) succinate, mono Mono (2-acryloyloxyethyl) phthalate mono (2-methacryloyloxyethyl), and the like. The unsaturated polycarboxylic acid may be a mono (meth) acrylate of the both terminal dicarboxylic polymers thereof, and examples thereof include ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate. have. Examples of the unsaturated carboxylic acid include acrylic acid-2-carboxyethyl ester, methacrylic acid-2-carboxyethyl ester, maleic acid monoalkyl ester, fumaric acid monoalkyl ester and 4-carboxystyrene.

Among them, acrylic acid, methacrylic acid, 2- (meth) acryloyl (meth) acrylate and the like are preferable for the purpose of forming the structural unit (a1-1-1) derived from an unsaturated carboxylic acid or the like having at least one carboxyl group in the above- (Meth) acryloyloxyethylhexahydrophthalic acid, 2- (meth) acryloyloxyethylphthalic acid, or an anhydride of an unsaturated polycarboxylic acid, and the like, and acrylic acid, metha It is more preferable to use acrylic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid.

The structural unit (a1-1-1) derived from an unsaturated carboxylic acid or the like having at least one carboxyl group in the molecule may be composed of one kind alone, or two or more kinds.

<<< (a1-1-2) Constituent units having both structures derived from an ethylenic unsaturated group and an acid anhydride >>>

The structural unit (a1-1-2) having both the ethylenic unsaturated group and the structure derived from an acid anhydride is preferably a unit derived from a monomer obtained by reacting a hydroxyl group and an acid anhydride present in a structural unit having an ethylenic unsaturated group.

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

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

- acid decomposable group which can be used for the structural unit (a1-1)

As the acid decomposable group that can be used for the structural unit (a1-1) having a protected carboxyl group protected with the acid decomposable group, the acid decomposable group may be used.

Among these acid decomposable groups, the carboxyl group is preferably a protected carboxyl group protected in the form of an acetal from the viewpoints of the basic physical properties of the photosensitive resin composition, particularly from the viewpoints of sensitivity and pattern shape, contact hole formation, and storage stability of the photosensitive resin composition. Among the acid decomposable groups, from the viewpoint of sensitivity, it is more preferable that the carboxyl group is a protected carboxyl group protected in the form of an acetal represented by the following formula (a1-10). When the carboxyl group is a protected protected carboxyl group in the form of an acetal represented by the following formula (a1-10), the protected carboxyl group as a whole has a structure of - (C = O) -O-CR ¹⁰¹ R ¹⁰² (OR ¹⁰³ ) .

[In the formula (a1-10), R ¹⁰¹ and R ¹⁰² each independently represent a hydrogen atom or an alkyl group, provided that R ¹⁰¹ and R ¹⁰² are not both hydrogen atoms. R ¹⁰³ represents an alkyl group. R ¹⁰¹ or R ¹⁰² and R ¹⁰³ may be connected to form a cyclic ether)

In the formula (a1-10), R ¹⁰¹ to R ¹⁰³ each independently represent a hydrogen atom or an alkyl group, and the alkyl group may be any of linear, branched and cyclic. Here, both of R ¹⁰¹ and R ¹⁰² do not represent a hydrogen atom, and at least one of R ¹⁰¹ and R ¹⁰² represents an alkyl group.

When R ¹⁰¹ , R ¹⁰² and R ¹⁰³ in the formula (a1-10) represent an alkyl group, the alkyl group may be any of linear, branched or cyclic.

The straight-chain or branched-chain alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 4 carbon atoms. Specific examples include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec- Butyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group and n-decyl group.

The cyclic alkyl group preferably has 3 to 12 carbon atoms, more preferably 4 to 8 carbon atoms, and still more preferably 4 to 6 carbon atoms. Examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group and an isobonyl group.

The alkyl group may have a substituent, and examples of the substituent include a halogen atom, an aryl group, and an alkoxy group. When a halogen atom is used as a substituent, R ¹⁰¹ , R ¹⁰² and R ¹⁰³ are haloalkyl groups. When an aryl group is used as a substituent, R ¹⁰¹ , R ¹⁰² and R ¹⁰³ are an aralkyl group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and among these, a fluorine atom or a chlorine atom is preferable.

The aryl group is preferably an aryl group having 6 to 20 carbon atoms, and more preferably an aryl group having 6 to 12 carbon atoms. Specific examples thereof include a phenyl group, an? -Methylphenyl group and a naphthyl group. Examples of the alkyl group substituted with an aryl group, that is, an aralkyl group include benzyl group,? -Methylbenzyl group, phenethyl group and naphthylmethyl group have.

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

When the alkyl group is a cycloalkyl group, the cycloalkyl group may have a linear or branched alkyl group having 1 to 10 carbon atoms as a substituent. When the alkyl group is a straight chain or branched chain alkyl group, Or a cycloalkyl group having 1 to 12 carbon atoms.

These substituents may be further substituted by the above substituents.

When R ¹⁰¹ , R ¹⁰² and R ¹⁰³ in the formula (a1-10) represent an aryl group, the aryl group preferably has 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms. The aryl group may have a substituent, and as the substituent, an alkyl group having 1 to 6 carbon atoms is preferably exemplified. As the aryl group, for example, a phenyl group, a tolyl group, a xylyl group, a cumenyl group, a 1-naphthyl group and the like can be mentioned.

Further, R ¹⁰¹ , R ¹⁰² and R ¹⁰³ may be bonded to each other to form a ring together with the carbon atoms to which they are bonded. Examples of the ring structure in the case where R ¹⁰¹ and R ¹⁰² , R ¹⁰¹ and R ¹⁰³ or R ¹⁰² and R ¹⁰³ are bonded include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a tetrahydrofuranyl group, An adamantyl group, and a tetrahydropyranyl group.

In the formula (a1-10), it is preferable that either R ¹⁰¹ or R ¹⁰² is a hydrogen atom or a methyl group.

The radically polymerizable monomer used for forming the constituent unit having a protective carboxyl group represented by the above formula (a1-10) may be commercially available or may be synthesized by a known method. For example, it can be synthesized by the synthesis method described in paragraphs 0037 to 0040 of Japanese Patent Laid-Open Publication No. 2011-221494.

The first preferred form of the structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group is a structural unit represented by the following formula.

(Wherein, R ¹ and R ² each independently represents a hydrogen atom, an alkyl group or an aryl group, and either one of the at least R ¹ and R ² alkyl group or aryl group, R ³ represents an alkyl group or an aryl group, R ¹ or R ² and R ³ may be connected to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X represents a single bond or an arylene group)

When R ¹ and R ² are an alkyl group, an alkyl group having 1 to 10 carbon atoms is preferred. When R ¹ and R ² are aryl groups, a phenyl group is preferred. R ¹ and R ² are each independently preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

R ³ represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms.

X represents a single bond or an arylene group, with a single bond being preferred.

A second preferred form of the structural unit (a1-1) having a protected carboxyl group protected with the acid-decomposable group is a structural unit represented by the following formula.

(Wherein R ¹²¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, L ¹ represents a carbonyl group or a phenylene group, and R ¹²² to R ¹²⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms)

R ¹²¹ is preferably a hydrogen atom or a methyl group.

L ¹ is preferably a carbonyl group.

R ¹²² to R ¹²⁸ are preferably a hydrogen atom.

Preferable specific examples of the structural unit (a1-1) having a protected carboxyl group protected with the acid-decomposable group include the following structural units. R represents a hydrogen atom or a methyl group.

<< (a1-2) Structural unit having a protective phenolic hydroxyl group protected by an acid-decomposable group >>

The structural unit (a1-2) having a protected phenolic hydroxyl group protected by the acid-decomposable group is a structural unit having a protected phenolic hydroxyl group, the structural unit having a phenolic hydroxyl group being protected by an acid-decomposable group described in detail below.

<<< (a1-2-1) Structural unit having a phenolic hydroxyl group >>>

Examples of the structural unit having a phenolic hydroxyl group include a hydroxystyrene-based structural unit and a structural unit in a novolak-based resin. Of these structural units, a structural unit derived from hydroxystyrene or -methylhydroxystyrene is It is preferable from the viewpoint of sensitivity. The structural unit represented by the following formula (a1-20) as a structural unit having a phenolic hydroxyl group is also preferable from the viewpoint of sensitivity.

Wherein R ²²⁰ represents a hydrogen atom or a methyl group, R ²²¹ represents a single bond or a divalent linking group, R ²²² represents a halogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms , a represents an integer of 1 to 5, b represents an integer of 0 to 4, and a + b is 5 or less. When two or more R ²²² are present, these R ²²² may be the same or different and may be the same)

In the formula (a1-20), R ²²⁰ represents a hydrogen atom or a methyl group, and is preferably a methyl group.

R ²²¹ represents a single bond or a divalent linking group. In the case of single-crystal combination, it is preferable since the sensitivity can be improved and the transparency of the cured film can be improved. Examples of the divalent linking group of R ²²¹ include alkylene groups and specific examples of R ²²¹ is an alkylene group include a methylene group, an ethylene group, a propylene group, an isopropylene group, an n-butylene group, an isobutylene group, Pentylene group, isopentylene group, neopentylene group, hexylene group and the like. Among them, R &lt; ²²¹ &gt; is preferably a single bond, a methylene group or an ethylene group. The divalent linking group may have a substituent, and examples of the substituent include a halogen atom, a hydroxyl group, and an alkoxy group. Although a represents an integer of 1 to 5, a is preferably 1 or 2, and more preferably a is 1, from the viewpoint of the effects of the present invention and easiness of production.

It is preferable that the bonding position of the hydroxyl group in the benzene ring is bonded to the 4-position when the carbon atom bonded to R ²²¹ is the reference (1 position).

R ²²² each independently represents a halogen atom or a straight or branched alkyl group having 1 to 5 carbon atoms. Specific examples include a fluorine atom, a chlorine atom, a bromine atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert- butyl group, a pentyl group, an isopentyl group and a neopentyl group . Among them, a chlorine atom, a bromine atom, a methyl group or an ethyl group is preferable in view of easiness of production.

B represents 0 or an integer of 1 to 4;

- acid decomposable group which can be used for the structural unit (a1-2)

The acid decomposable group which can be used for the structural unit (a1-2) having a protected phenolic hydroxyl group protected by the acid-decomposable group is preferably an acid decomposable group which can be used for the structural unit (a1-1) having a protected carboxyl group protected with the acid- As well as the acid-decomposable group, known ones can be used, and they are not particularly limited. Among the acid decomposable groups, structural units having a protective phenolic hydroxyl group protected by an acetal are preferred from the viewpoints of basic physical properties of the photosensitive resin composition, particularly from the viewpoints of sensitivity and pattern shape, storage stability of the photosensitive resin composition, and formability of contact holes. Among the acid decomposable groups, from the viewpoint of sensitivity, it is more preferable that the phenolic hydroxyl group is a protected phenolic hydroxyl group protected in the form of an acetal represented by the above formula (a1-10). When the phenolic hydroxyl group is a protected protected phenolic hydroxyl group in the form of an acetal represented by the above formula (a1-10), as a whole of the protected phenolic hydroxyl group, -Ar-O-CR ¹⁰¹ R ¹⁰² (OR ¹⁰³ ) Structure. Ar represents an arylene group.

Preferable examples of the acetal ester structure of the phenolic hydroxyl group may include a combination of R ¹⁰¹ = R ¹⁰² = R ¹⁰³ = methyl group, or a combination of R ¹⁰¹ = R ¹⁰² = methyl group and R ¹⁰³ = benzyl group.

Examples of the radically polymerizable monomer used to form a structural unit having a protected phenolic hydroxyl group in which the phenolic hydroxyl group is protected in the form of an acetal include those described in paragraph 0042 of JP-A No. 2011-215590 .

Of these, a 1-alkoxyalkyl protected derivative of 4-hydroxyphenyl methacrylate and a tetrahydropyranyl protected derivative of 4-hydroxyphenyl methacrylate are preferred from the viewpoint of transparency.

Specific examples of the acetal protecting group of the phenolic hydroxyl group include 1-alkoxyalkyl groups, and examples thereof include a 1-ethoxyethyl group, a 1-methoxyethyl group, a 1-n-butoxyethyl group, 1-cyclohexyloxy) ethyl group, 1- (2-cyclohexyloxy) ethyl group, 1-naphthyloxy group, Oxyethyl group, etc. These may be used singly or in combination of two or more kinds.

The radically polymerizable monomer used for forming the structural unit (a1-2) having a protected phenolic hydroxyl group protected with the acid-decomposable group may be commercially available or may be synthesized by a known method. For example, a compound having a phenolic hydroxyl group can be synthesized by reacting with a vinyl ether in the presence of an acid catalyst. The above-mentioned synthesis may be carried out by previously copolymerizing a monomer having a phenolic hydroxyl group with another monomer, and then reacting with a vinyl ether in the presence of an acid catalyst.

Specific examples of the structural unit (a1-2) having a protected phenolic hydroxyl group protected by the acid-decomposable group include the following structural units, but the present invention is not limited thereto. In the following specific examples, R represents a hydrogen atom or a methyl group.

- Preferred form of the structural unit (a1)

When the polymer having the structural unit (a1) does not substantially contain the structural unit (a2), the structural unit (a1) is preferably 20 to 100 mol%, more preferably 30 to 90 mol% Mol% is more preferable.

When the polymer having the structural unit (a1) has the following structural unit (a2), the structural unit (a1) has a structural unit (a1) and a structural unit (a2) Mol%, more preferably 10 to 60 mol%. In particular, when the structural unit (a1) is a structural unit having a carboxyl group protected in the form of an acetal, the content is preferably 20 to 50 mol%.

In the present invention, when the content of the &quot; constituent unit &quot; is defined as the molar ratio, the above-mentioned &quot; constituent unit &quot; In the present invention, the &quot; monomer unit &quot; may be modified after polymerization by a polymer reaction or the like. The same applies to the following.

The structural unit (a1-1) having a protected carboxyl group protected with the acid-decomposable group is characterized in that the phenomenon is faster than that of the structural unit (a1-2) having a protected phenolic hydroxyl group protected by the acid decomposable group. Therefore, when a rapid development is desired, the structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group is preferable. On the contrary, when it is desired to slow the development, it is preferable to use the structural unit (a1-2) having a protected phenolic hydroxyl group protected with an acid-decomposable group.

The structural unit (a1-1) having a protected carboxyl group protected with the acid-decomposable group is characterized in that the phenomenon is faster than that of the structural unit (a1-2) having a protected phenolic hydroxyl group protected by the acid decomposable group. Therefore, when a rapid development is desired, the structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group is preferable. On the contrary, when it is desired to slow the development, it is preferable to use the structural unit (a1-2) having a protected phenolic hydroxyl group protected with an acid-decomposable group.

< (a2) Structural unit having a crosslinkable group >

Component A contains a polymer having a structural unit (a2) having a crosslinkable group. The crosslinking group is not particularly limited as long as it is a group that causes a curing reaction by a heat treatment. Preferable examples of the form of the structural unit having a crosslinkable group include a group represented by an epoxy group, oxetanyl group, -NH-CH ₂ -OR (R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms) and an ethylenic unsaturated group A structural unit containing at least one selected from the group consisting of an epoxy group, an oxetanyl group, and a group represented by -NH-CH ₂ -OR (R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms) And at least one selected is preferable. Among them, the photosensitive resin composition of the present invention preferably contains a constituent unit in which the component A contains at least one of an epoxy group and an oxetanyl group. More specifically, the following can be mentioned.

<< (a2-1) Structural unit having an epoxy group and / or an oxetanyl group >>

The component A preferably contains a polymer having a structural unit (structural unit (a2-1)) having an epoxy group and / or an oxetanyl group. The cyclic ether group of the 3-membered ring is also called an epoxy group, and the cyclic ether group of the 4-membered ring is also called an oxetanyl group.

The structural unit (a2-1) having an epoxy group and / or an oxetanyl group may have at least one epoxy group or oxetanyl group in one structural unit, and may contain at least one epoxy group and at least one oxetanyl group, Or an oxetanyl group. The epoxy group and / or the oxetanyl group is preferably, but not limited to, a total of 1 to 3 epoxy groups and / or an oxetanyl group, and the epoxy group and / More preferably an epoxy group or an oxetanyl group, and still more preferably one epoxy group or oxetanyl group.

Specific examples of the radical polymerizable monomer used for forming the structural unit having an epoxy group include glycidyl acrylate, glycidyl methacrylate, glycidyl? -Ethyl acrylate, glycidyl? -N-propyl acrylate Dicyclohexylmethyl acrylate, glycidyl alpha-n-butyl acrylate, 3,4-epoxybutyl acrylate, methacrylic acid-3,4-epoxybutyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, -Epoxy cyclohexylmethyl,? -Ethylacrylic acid-3,4-epoxycyclohexylmethyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, Compounds having an alicyclic epoxy skeleton described in paragraphs [0031] to [00300] of Japanese Patent No. 4168443, and the like.

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

Specific examples of the radically polymerizable monomer used to form the structural unit (a2-1) having an epoxy group and / or an oxetanyl group include monomers containing a methacrylate ester structure and monomers containing an acrylate ester structure desirable.

Among these, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, methyl (3-ethyloxetan-3-yl) (3-ethyloxetan-3-yl) methyl. These structural units may be used singly or in combination of two or more.

Preferable specific examples of the structural unit (a2-1) having an epoxy group and / or an oxetanyl group include the following structural units. R represents a hydrogen atom or a methyl group.

<< (a2-2) Structural unit having an ethylenic unsaturated group >>

(A2-2) having an ethylenic unsaturated group as one of the structural units (a2) having a crosslinkable group (hereinafter also referred to as &quot; structural unit (a2-2) &quot;). As the structural unit (a2-2) having an ethylenically unsaturated group, a structural unit having an ethylenic unsaturated group at the side chain is preferable, a structural unit having an ethylenic unsaturated group at the end and a side chain having 3 to 16 carbon atoms is more preferable, And more preferably a structural unit having a side chain represented by the formula (a2-2-1).

Wherein R ³⁰¹ represents a divalent linking group of 1 to 13 carbon atoms, R ³⁰² represents a hydrogen atom or a methyl group, and the broken line portion represents a divalent linking group of a structural unit (a2) having a crosslinkable group Indicating the site to be connected]

R ³⁰¹ is a divalent linking group having 1 to 13 carbon atoms, which may include an alkenyl group, a cycloalkenyl group, an arylene group, or a combination thereof, and may include a bond such as an ester bond, an ether bond, an amide bond or a urethane bond . The divalent linking group may have a substituent such as a hydroxyl group or a carboxyl group at an arbitrary position. Specific examples of R ³⁰¹ include the following divalent linking groups.

Among the side chains represented by the above formula (a2-2-1), aliphatic side chains including the divalent linking group represented by R ³⁰¹ are preferable.

In addition, for the structural unit having an ethylenic unsaturated group (a2-2), reference may be made to the description in paragraphs 0072 to 0090 of Japanese Patent Laid-Open Publication No. 2011-215580.

<< Constituent unit having a group represented by the formula (a2-3) -NH-CH ₂ -OR (R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms) >>

The copolymer used in the present invention is also preferably a structural unit (a2-3) having a group represented by -NH-CH ₂ -OR (R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms). By having the constituent unit (a2-3), a curing reaction can be caused by a gentle heat treatment, and a cured film excellent in various properties can be obtained. Here, R is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 9 carbon atoms, and still more preferably an alkyl group having 1 to 4 carbon atoms. The alkyl group may be any of linear, branched or cyclic alkyl groups, but is preferably a linear or branched alkyl group. The structural unit (a2) is more preferably a structural unit having a group represented by the following formula (a2-30).

[Wherein, in formula (a2-30), R ³¹ represents a hydrogen atom or a methyl group, and R ³² represents an alkyl group having 1 to 20 carbon atoms]

R ³² is preferably an alkyl group having 1 to 9 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms. The alkyl group may be any of linear, branched or cyclic alkyl groups, but is preferably a linear or branched alkyl group.

Specific examples of R ³² include a methyl group, an ethyl group, an n-butyl group, an i-butyl group, a cyclohexyl group, and an n-hexyl group. Of these, an i-butyl group, an n-butyl group and a methyl group are preferable.

- Preferred form of the structural unit (a2)

When the polymer having the structural unit (a2) does not substantially contain the structural unit (a1), the structural unit (a2) is preferably from 5 to 90 mol%, more preferably from 20 to 80 mol% Mol% is more preferable.

When the polymer having the structural unit (a2) has the structural unit (a1), the structural unit (a2) is a polymer having the structural unit (a1) and the structural unit (a2) Is preferably 70 mol%, more preferably 10 mol% to 60 mol%.

In the present invention, regardless of the form, the content of the structural unit (a2) in the total structural units of the component (A) is preferably 3 to 70 mol%, more preferably 10 to 60 mol%.

Within the above range, the transparency and chemical resistance of the cured film obtained from the photosensitive resin composition are improved.

<(a3) Other structural units>

In the present invention, the component A may have other constituent units (a3) other than the above-mentioned constituent units (a1) and / or (a2). These constituent units may include the polymer components (1) and / or (2). Apart from the polymer component (1) or (2), a polymer component containing substantially no structural unit (a1) and structural unit (a2) and having another structural unit (a3) may be contained. (A1) and (a2) other than the polymer component (1) or (2), the amount of the polymer component to be blended is not particularly limited so long as it contains a polymer component having another constituent unit Is preferably 60 mass% or less, more preferably 40 mass% or less, and most preferably 20 mass% or less, of the total polymer components.

The monomer to be the other constituent unit (a3) is not particularly limited and includes, for example, styrenes, alkyl (meth) acrylates, cyclic alkyl (meth) acrylate esters, (meth) acrylic acid aryl esters, unsaturated dicarboxylic acid di An unsaturated aromatic compound, a conjugated diene compound, an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, an unsaturated dicarboxylic acid anhydride, and other unsaturated compounds. Further, as described later, it may have a structural unit having an acid group. The monomers to be the other constituent unit (a3) may be used alone or in combination of two or more.

Hereinafter, preferred embodiments of the polymer component in the present invention are described, but the present invention is not limited thereto.

- First Embodiment -

Wherein the polymer component (1) further comprises one or more other structural units (a3).

- Second Embodiment -

(A1) a form in which the polymer having a constituent unit having a group protected with an acid-decomposable group further comprises one or more other constituent units (a3) in the polymer component (2).

- Third Embodiment -

The form (a2) of the polymer component (2) further comprises one or more other structural units (a3) having a structural unit having a crosslinkable group.

- Fourth Embodiment -

In any one of the first to third embodiments, the structural unit having at least an acid group as the other structural unit (a3) in any one of the polymers.

- Fifth Embodiment -

A form having a polymer having substantially no structural unit (a1) and structural unit (a2) and further having another structural unit (a3), apart from the polymer component (1) or (2).

- Sixth Embodiment -

A mode formed by combining two or more of the first to fifth embodiments.

Specific examples of the structural unit (a3) include styrene, tert-butoxystyrene, methylstyrene, hydroxystyrene,? -Methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinylbenzoate, (Meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, Acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, acrylonitrile, ethylene glycol monoacetoacetate mono And the like. In addition, the compounds described in paragraphs 0021 to 0024 of Japanese Patent Application Laid-Open No. 2004-264623 can be mentioned.

As the other structural unit (a3), structural units derived from a styrene or a monomer having an alicyclic cyclic skeleton are preferable from the viewpoint of electrical characteristics. Specific examples thereof include styrene, tert-butoxystyrene, methylstyrene, hydroxystyrene,? -Methylstyrene, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, isobonyl (Meth) acrylate, and the like.

As the other structural unit (a3), a structural unit derived from a (meth) acrylic acid alkyl ester is preferable from the viewpoint of adhesion. Specific examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate and n-butyl (meth) acrylate. More preferred is methyl (meth) acrylate. The content of the structural unit (a3) among the structural units constituting the polymer is preferably 60 mol% or less, more preferably 50 mol% or less, still more preferably 40 mol% or less. The lower limit value may be 0 mol%, but is preferably 1 mol% or more, for example, and is more preferably 5 mol% or more. Within the range of the above-mentioned numerical values, various properties of the cured film obtained from the photosensitive resin composition are improved.

The polymer contained in the component A preferably has a structural unit having an acid group as the other structural unit (a3). When the polymer has an acid group, the polymer easily dissolves in an alkaline developing solution, and the effect of the present invention is more effectively exhibited. The acid group in the present invention means a proton dissociable group having a pKa of less than 10.5. The acid group is introduced into the polymer as a constituent unit containing an acid group by using a monomer capable of forming an acid group. By incorporating such a structural unit containing an acid group in the polymer, it tends to be easily soluble in an alkaline developer.

Examples of the acid group used in the present invention include those derived from a carboxylic acid group, those derived from a sulfonamide group, those derived from a phosphonic acid group, those derived from a sulfonic acid group, those derived from a phenolic hydroxyl group, sulfonamide groups, An imide group and the like, and those derived from a carboxylic acid group and / or a phenolic hydroxyl group are preferred.

The structural unit containing an acid group used in the present invention is more preferably a structural unit derived from styrene, a structural unit derived from a vinyl compound, and (meth) acrylic acid and / or an ester thereof.

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

The constituent unit having an acid group is preferably from 1 to 80 mol%, more preferably from 1 to 50 mol%, still more preferably from 5 to 40 mol%, and particularly preferably from 5 to 30 mol% of the constituent units of the entire polymer component , And particularly preferably from 5 to 20 mol%.

When the resin corresponding to the component A contains a structural unit having an acid group, the acid value of the resin is preferably from 20 to 100 mgKOH / g, more preferably from 30 to 80 mgKOH / g, MgKOH / g is more preferable.

In the present invention, in addition to the polymer component (1) or (2), a polymer having substantially no structural unit (a1) and / or structural unit (a2) and having another structural unit (a3) may be contained.

As such a polymer, a resin having a carboxyl group in the side chain is preferable. For example, Japanese Patent Application Laid-Open No. 59-44615, Japanese Patent Publication No. 54-34327, Japanese Patent Publication No. 58-12577, Japanese Patent Publication No. 54-25957, Japanese Patent Application Laid-open No. 59-53836, Methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers and the like as disclosed in the respective publications of Japanese Patent Application Laid-Open No. 59-71048 Acidic cellulose derivatives having a carboxyl group in a side chain, acid anhydride added to a polymer having a hydroxyl group, and the like, and a polymer having a (meth) acryloyl group in the side chain is also preferable.

(Meth) acrylate / (meth) acrylic acid copolymer, 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / (Meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / Benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl Methacrylate / methacrylic acid copolymer, and the like.

In addition, Japanese Patent Application Laid-Open Nos. 7-207211, 8-259876, 10-300922, 11-140144, 11-174224 A publicly known polymer compound described in Japanese Patent Application Laid-Open Nos. 2000-56118, 2003-233179, and 2009-52020 can be used.

These polymers may contain only one kind or two or more kinds.

As these polymers, commercially available SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P, SMA 3840F (manufactured by Satoruma Corporation), ARUFON UC-3000, ARUFON UC-3510, ARUFON UC- JUNCRYL 678, JONCRYL 67, JONCRYL 586 (manufactured by BASF), etc. may be used as the ultraviolet ray absorber.

The molecular weight of the polymer in component A -

The molecular weight of the polymer in the component A is a polystyrene reduced weight average molecular weight, preferably 1,000 to 200,000, more preferably 2,000 to 50,000. Within the range of the above numerical values, various characteristics are good. The ratio (dispersion degree, Mw / Mn) of the number average molecular weight Mn to the weight average molecular weight Mw is preferably from 1.0 to 5.0, more preferably from 1.5 to 3.5.

- Method of preparing polymer in component A -

Various methods are also known for the method of synthesizing the polymer in the component A. For example, a radical containing a radical polymerizable monomer used for forming at least the structural unit (a1) and the structural unit (a3) Can be synthesized by polymerization of a polymerizable monomer mixture in an organic solvent using a radical polymerization initiator. It may also be synthesized by a so-called polymer reaction.

The content of the component A in the photosensitive resin composition of the present invention is preferably 20 to 99.9% by mass, more preferably 50 to 98% by mass, and more preferably 70 to 95% by mass based on the total solid content of the photosensitive resin composition More preferable. When the content is within this range, the pattern forming property upon development becomes good. The solid content of the photosensitive resin composition refers to an amount excluding volatile components such as a solvent.

(Component S) A dispersant having at least one acid group represented by the formula (S)

The resin composition of the present invention (component S) is represented by the following formula (S) and contains a dispersant having at least one acid group. By containing the component S, the resin composition of the present invention can form a cured product having a high refractive index and excellent transparency since there are few coarse particles at the time of dispersion of the metal oxide particles and no aggregation when the dispersion and the polymer component are mixed.

(In the formula (S), R ³ represents a linking group of (m + n), R ⁴ and R ⁵ each independently represent a single bond or a divalent linking group, A ² represents an organic pigment structure, , A group having a basic nitrogen atom, a urea group, a urethane group, a group having a radial oxygen atom, an alkoxysilyl group, a phenol group, an alkyl group, an aryl group, a group having an alkyleneoxy group, an imide group, an alkyloxycarbonyl group, A monovalent organic group containing at least one partial structure selected from the group consisting of an aminocarbonyl group, a carboxylate group, a sulfonamide group, an epoxy group, an isocyanate group and a hydroxyl group, n A ² and R ⁴ may be the same or different, m represents 0 to 8, n represents 2 to 9, m + n represents 3 to 10, P ² represents a polymer skeleton, and m P ² and R ⁵ may be the same or different)

Component S is a dispersant having at least one acid group. By having an acid group, it is presumed to act as an adsorbent for the metal oxide particles, and the dispersibility of the metal oxide particles is excellent.

Examples of the acid group include a carboxylic acid group (carboxyl group), a sulfonic acid group, a phosphoric acid group, a phenolic hydroxyl group and the like, and from the viewpoint of the adsorptivity and dispersibility into metal oxide particles, at least one kind selected from the group consisting of carboxylic acid group, And a carboxylic acid group is particularly preferable. The acid groups in the above-mentioned dispersant may be contained singly or in combination of two or more kinds.

The acid group in the component S may have any structure of the formula (S). Specifically, for example, acid groups may be included in A ² in the formula (S), also it may be contained in the polymer skeleton represented by P ^2, but may be included in both of the A ² and P ^2, effect from the point of view it is preferably included in a ^2.

In formula (S), A ² represents an organic dye structure, a heterocyclic structure, an acid group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a saturated oxygen atom, an alkoxysilyl group, At least one partial structure selected from the group consisting of an aryl group, an alkyleneoxy group, an imide group, an alkyloxycarbonyl group, an alkylaminocarbonyl group, a carboxylate group, a sulfonamide group, an epoxy group, an isocyanate group, and a hydroxyl group &Lt; / RTI &gt; In the formula (S), A ² in which n are present may be the same or different.

That is, A ² is a structure having adsorptivity to metal oxide particles such as an organic dye structure and a heterocyclic structure, a structure having an acid group, a group having a basic nitrogen atom, a urea group, a urethane group, A metal oxide such as a silyl group, a phenol group, an alkyl group, an aryl group, an alkyleneoxy group, an imide group, an alkyloxycarbonyl group, an alkylaminocarbonyl group, a carboxylate group, a sulfonamide group, an epoxy group, an isocyanate group, Represents a monovalent organic group containing at least one functional group having adsorptivity to particles.

Hereinafter, the partial structure (structure and functional group) having adsorptivity to the metal oxide particles will be collectively referred to as &quot; adsorption site &quot;.

The adsorption site may contain at least one of A ² , and may include two or more species.

In the present invention, the "monovalent organic group containing at least one adsorption site" is a monovalent organic group having 1 to 200 carbon atoms, 0 to 20 nitrogen atoms, 0 to 100 oxygen atoms, 1 To 400 hydrogen atoms, and a linking group formed from 0 to 40 sulfur atoms. In addition, when the adsorption site itself can constitute a monovalent organic group, it may be a monovalent organic group in which the adsorption site itself is represented by A ² .

First, the adsorption sites constituting A ² will be described below.

The term "organic pigment structure" as used herein refers to, for example, phthalocyanine, insoluble azo, azo lake, anthraquinone, quinacridone, dioxadine, diketopyrrolopyrrole, anthrapyridine, Preferable examples of the dye structure of the phthalocyanine-based, flavanthrone-based, perinone-based, perylene-based and thioindigo-based pigments are phthalocyanine, azo lake, anthraquinone, dioxadine and diketopyrrolopyrrole pigment structures Is more preferable, and a dye structure of phthalocyanine type, anthraquinone type, and diketopyrrolopyrrole type is particularly preferable.

The "heterocyclic structure" may be a group having at least one heterocyclic ring. The hetero atom in the above "heterocyclic structure" preferably contains at least one of O (oxygen atom), N (nitrogen atom), or S (sulfur atom) More preferable. The heterocyclic ring in the above "heterocyclic structure" includes, for example, thiophene, furan, xanthene, pyrrole, pyrroline, pyrrolidine, dioxolane, pyrazole, pyrazoline, pyrazolidine, imidazole, Wherein the substituent is selected from the group consisting of a hydrogen atom, a hydroxyl group, a hydroxyl group, a hydroxyl group, a hydroxyl group, a hydroxyl group, a hydroxyl group, a hydroxyl group, Heterocyclic ring selected from the group consisting of indolinone, benzimidazolone, benzothiazole, succinimide, phthalimide, naphthalimide, hydantoin, indole, quinoline, carbazole, acridine, And examples thereof include pyrrole, pyrrolidine, pyrazole, pyrazoline, pyrazolidine, imidazole, triazole, pyridine, piperidine, morpholine, pyridazine, pyrimidine, Azine, isoindolin, isoindolinone, benzimadolone, benzothiazole, succinimide , Phthalimide, naphthalimide, hydantoin, carbazole, acridine, and O is more preferably a heterocyclic ring selected from the group consisting of chestnut money.

The above "organic dye structure" or "heterocyclic structure" may further have a substituent. Examples of the substituent include substituents such as an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, a phenyl group, a naphthyl group, An alkoxy group having 1 to 20 carbon atoms such as an alkoxy group having 1 to 6 carbon atoms such as an aryl group, a hydroxyl group, an amino group, a carboxyl group, a sulfonamide group, an N-sulfonylamide group or an acetoxy group, A halogen atom such as a chlorine atom or a bromine atom, a carbonic ester group such as an alkoxycarbonyl group having 2 to 7 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group or a cyclohexyloxycarbonyl group, a cyano group or a t-butylcarbonate group . Here, these substituents may be bonded to the organic dye structure or the heterocyclic structure through a linking group composed of the following structural unit or a combination of the structural units.

The "acid group" includes, for example, a carboxylic acid group, a sulfonic acid group, a monosulfuric acid ester group, a phosphoric acid group, a monophosphoric acid ester group and a boric acid group as preferable examples, and a carboxylic acid group, a sulfonic acid group, , A mono phosphate ester group is more preferable, and a carboxylic acid group, a sulfonic acid group and a phosphoric acid group are more preferable, and a carboxylic acid group is particularly preferable.

The above-mentioned "group having a basic nitrogen atom" includes, for example, an amino group (-NH ₂ ), a substituted imino group (-NHR ⁸ , -NR ⁹ R ¹⁰ wherein R ⁸ , R ⁹ and R ¹⁰ are Independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, an aralkyl group having 7 or more carbon atoms, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms) A guanidyl group represented by the following formula (a1), and an amidinyl group represented by the following formula (a2).

In formula (a1), R ¹¹ and R ¹² each independently represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms.

In formula (a2), R ¹³ and R ¹⁴ each independently represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms.

Among them, an amino group (-NH ₂ ), a substituted imino group (-NHR ⁸ , -NR ⁹ R ¹⁰ , wherein R ⁸ , R ⁹ and R ¹⁰ each independently represent an alkyl group having 1 to 10 carbon atoms, a phenyl group or a benzyl group And a guanidyl group represented by the formula (a1): wherein R ¹¹ and R ¹² each independently represent an alkyl group having 1 to 10 carbon atoms, a phenyl group or a benzyl group; (Wherein R ¹³ and R ¹⁴ each independently represent an alkyl group having 1 to 10 carbon atoms, a phenyl group or a benzyl group), and the like are more preferable.

In particular, an amino group (-NH ₂ ), a substituted imino group (-NHR ⁸ , -NR ⁹ R ¹⁰ , wherein R ⁸ , R ⁹ and R ¹⁰ each independently represent an alkyl group having 1 to 5 carbon atoms, a phenyl group or a benzyl group) , Guanidyl group represented by the formula (a1) [in the formula (a1), R ¹¹ and R ¹² each independently represent an alkyl group having 1 to 5 carbon atoms, a phenyl group or a benzyl group] An amidinyl group [in the formula (a2), R ¹³ and R ¹⁴ each independently represents an alkyl group having 1 to 5 carbon atoms, a phenyl group or a benzyl group].

Examples of the "urea" include -NR ¹⁵ CONR ¹⁶ R ¹⁷ wherein R ¹⁵ , R ¹⁶ and R ¹⁷ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, Preferred is an aralkyl group having 7 or more carbon atoms and is preferably an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms), -NR ¹⁵ CONHR ¹⁷ , R ¹⁵ and R ¹⁷ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, and more preferably -NHCONHR ¹⁷ (Wherein R ¹⁷ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms, and includes an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, &Lt; / RTI &gt; preferably an aralkyl group of &lt; RTI ID = 0.0 &gt; Is recommended.

Examples of the "urethane group" include -NHCOOR ¹⁸ , -NR ¹⁹ COOR ²⁰ , -OCONHR ²¹ , -OCONR ²² R ²³ (wherein R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² and R ²³ Each independently represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms, and is preferably an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms it is preferable) and the like as a preferable example, -NHCOOR ^18, -OCONHR ²¹ (here, R ¹⁸ and R ²¹ are each independently an alkyl group of 1 to 20 carbon atoms, having a carbon number of 6 or more aryl groups, or aralkyl having a carbon number of 7 or more More preferably an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms), -NHCOOR ¹⁸ , -OCONHR ²¹ (wherein R ¹⁸ And R &lt; ²¹ &gt; each independently represent an alkyl group having from 1 to 10 carbon atoms, an aryl group having from 6 to 12 carbon atoms, An aralkyl group having 7 to 10 carbon atoms) and the like are particularly preferable.

Examples of the "group having a radial oxygen atom" include an acetylacetonate group, a group having a crown ether structure, and the like.

Examples of the "alkoxysilyl group" include a trimethoxysilyl group, a triethoxysilyl group, and the like.

The alkyl group represented by the substituent A ^{2 may} be linear or branched, preferably an alkyl group having 1 to 40 carbon atoms, more preferably an alkyl group having 4 to 30 carbon atoms, and still more preferably an alkyl group having 10 to 18 carbon atoms.

The aryl group represented by the substituent A ² is preferably an aryl group having 6 to 10 carbon atoms.

As the above-mentioned "group having an alkyleneoxy group", a group having a polyalkyloxy group at the terminal is preferable, and the alkyloxy group preferably has 2 to 20 carbon atoms. The alkyleneoxy chain is not particularly limited as far as it has at least one alkyleneoxy group, but is preferably composed of an alkyleneoxy group having 2 to 6 carbon atoms. Examples of the alkyleneoxy group include -CH ₂ CH ₂ O-, -CH ₂ CH ₂ CH ₂ O- and the like.

The alkyl moiety in the "alkyloxycarbonyl group" is preferably an alkyl group having 1 to 20 carbon atoms.

The alkyl moiety in the "alkylaminocarbonyl group" is preferably an alkyl group having 1 to 20 carbon atoms.

Examples of the "carboxylic acid base" include groups such as an ammonium salt of a carboxyl group.

As the "sulfonamide group", the hydrogen atom bonded to the nitrogen atom of the sulfonamide structure may be substituted with an alkyl group (methyl group, etc.), an acyl group (acetyl group, trifluoroacetyl group, etc.)

In particular, A ² is preferably a monovalent substituent group having at least one functional group having a pKa of 5 or more from the viewpoint of improving the interaction with the metal oxide particles, improving the refractive index, and decreasing the viscosity of the composition. More preferably a monovalent substituent having at least one functional group of -14.

The term &quot; pKa &quot; used herein is a definition described in the Chemical Manual (II) (revised edition 4, 1993, edited by The Japan Chemical Society, Maruzen Co., Ltd.).

Examples of the functional group having a pKa of 5 or more include a group having a saturated oxygen atom, a group having a basic nitrogen atom, a phenol group, a urea group, a urethane group, an alkyl group, an aryl group, an alkyloxycarbonyl group, an alkylaminocarbonyl group, , An imide group, a carboxylic acid group, a sulfonamide group, a hydroxyl group, and a heterocyclic group.

Specific examples of the functional group having a pKa of 5 or more include phenol groups (pKa about 8 to 10), alkyl groups (pKa about 46 to about 53), aryl groups (about pKa about 40 to 43) -COCH ₂ CO- (pKa 8 to 10), sulfonamide group (pKa 9 to 11), hydroxyl group (pKa 15 to 17), complex Ventilation (about 12 to 30 pKa), and the like.

Among them, A ² is preferably a monovalent substituent having at least one group selected from the group consisting of an acid group, a urea group, a urethane group, a phenol group, a sulfonamide group, an imide group and a group having a saturated oxygen atom.

The linking group to be bonded to the adsorption site may be a single bond, or a single bond, or a single bond, or a single bond, or an alkylene group having 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, A linking group formed from a sulfur atom is preferable, and this linking group may be unsubstituted or may further have a substituent. Specific examples of the linking group include the following structural units or groups in which the structural units are combined.

When the linking group has a substituent, examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as methyl and ethyl, an aryl group having 6 to 16 carbon atoms such as a phenyl group and a naphthyl group, a hydroxyl group, an amino group, a carboxyl group, An alkoxy group having 1 to 6 carbon atoms such as a methoxy group and an ethoxy group, a halogen atom such as a chlorine atom and a bromine atom, a methoxycarbonyl group, a methoxycarbonyl group, An alkoxycarbonyl group having 2 to 7 carbon atoms such as an ethoxycarbonyl group and a cyclohexyloxycarbonyl group, a carbonic ester group such as a cyano group and a t-butylcarbonyl group, and the like.

Among them, A ^{2 represents} at least one partial structure selected from the group consisting of an organic dye structure, a heterocyclic structure, an acid group, a group having a basic nitrogen atom, a urea group, a phenol group, an alkyl group, an aryl group, and an alkyloxycarbonyl group Is preferably a monovalent organic group containing at least one acid group and particularly preferably a monovalent organic group containing at least one acid group.

As the component S, a compound in which A ² is only a monovalent organic group containing at least one acid group, or a monovalent organic group containing at least one acid group as A ² and an organic dye structure, a heterocyclic structure, an acid group, a basic nitrogen group having atom, a urea group, a phenol group, an alkyl group, an aryl group, and alkyloxycarbonyl group preferably a compound having a monovalent organic group containing at least one type of a partial structure selected from the group consisting of and, a ² is an acid group at least A compound having only a monovalent organic group including one kind is particularly preferable.

The A ² is more preferably a monovalent organic group represented by the following formula (4).

In the formula (4), B ¹ represents a group having an adsorption site (i.e., an organic pigment structure, a heterocyclic structure, an acid group, a group having a basic nitrogen atom, a urea group, a urethane group, A partial structure selected from the group consisting of a hydrocarbon group, an alkoxysilyl group, an epoxy group, an isocyanate group and a hydroxyl group), and R ²⁴ represents a single bond or a (a + 1) a represents an integer of 1 to 10, and B ¹ in a formula (4) may be the same or different.

The adsorption site represented by B ¹ is the same as the adsorption site constituting A ² in the formula (S), and preferable examples are also the same.

Among them, a partial structure selected from the group consisting of an organic dye structure, a heterocyclic structure, an acid group, a group having a basic nitrogen atom, a urea group, a phenol group, an alkyl group, an aryl group, and an alkyloxycarbonyl group is preferable, .

R ²⁴ represents a divalent connecting group or a single bond (a + 1), a represents an integer of 1 to 10, is an integer of 1-7, and preferably, and more preferably an integer of 1 to 5, an integer of 1 to 3 Is particularly preferable.

(a + 1) bond is formed from 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to 20 sulfur atoms, And may be unsubstituted or may further have a substituent.

Specific examples of the linking group (a + 1) include the following structural units or groups in which the structural units are combined (may form a cyclic structure).

R ^{24 is a} single bond or a single bond consisting of 1 to 50 carbon atoms, 0 to 8 nitrogen atoms, 0 to 25 oxygen atoms, 1 to 100 hydrogen atoms, and 0 to 10 sulfur atoms (a + 1), and is preferably a single bond, or a single bond, or a single bond, or a single bond, or a single bond, or a single bond, (A + 1) -valent linking group formed from 7 sulfur atoms, more preferably a single bond, or a single bond, or one to ten carbon atoms, 0 to 5 nitrogen atoms, 0 to 10 oxygen atoms, (A + 1) &lt; / RTI &gt; bridged group formed from 0 to 5 hydrogen atoms, and from 0 to 5 sulfur atoms.

When the (a + 1) th connecting group has a substituent, examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, an aryl group having 6 to 16 carbon atoms such as a phenyl group and a naphthyl group, , An acyloxy group having 1 to 6 carbon atoms such as a carboxyl group, a sulfonamide group, an N-sulfonylamide group and an acetoxy group, an alkoxy group having 1 to 6 carbon atoms such as a methoxy group and an ethoxy group, An alkoxycarbonyl group having 2 to 7 carbon atoms such as a halogen atom, a methoxycarbonyl group, an ethoxycarbonyl group and a cyclohexyloxycarbonyl group, and a carbonic ester group such as a cyano group and a t-butylcarbonate group.

In the formula (S), R ⁴ and R ⁵ each independently represent a single bond or a divalent linking group. The n R ⁴ present may be the same or different. R ⁵ present in m groups may be the same or different.

The divalent linking group in R ⁴ and R ⁵ is preferably a divalent linking group having 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to 20 A group formed from a sulfur atom, which may be unsubstituted or may further have a substituent.

As a specific example, the bivalent linking group includes a group formed by combining the following structural units or structural units thereof.

R ⁴ and R ⁵ are each independently a single bond or a straight or branched alkyl group having 1 to 50 carbon atoms, 0 to 8 nitrogen atoms, 0 to 25 oxygen atoms, 1 to 100 hydrogen atoms, and 0 to 10 A divalent linking group formed from sulfur atoms of 1 to 30 carbon atoms, 0 to 6 nitrogen atoms, 0 to 15 oxygen atoms, 1 to 50 hydrogen atoms, and More preferably a divalent linking group formed from 0 to 7 sulfur atoms, more preferably a single bond or an alkylene group having 1 to 10 carbon atoms, 0 to 5 nitrogen atoms, 0 to 10 oxygen atoms, 1 to 30 Hydrogen atoms, and divalent linking groups formed from 0 to 5 sulfur atoms are particularly preferred.

When the above bivalent connecting group has a substituent, examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, an aryl group having 6 to 16 carbon atoms such as a phenyl group and a naphthyl group, a hydroxyl group, An acyloxy group having 1 to 6 carbon atoms such as an amide group, an N-sulfonylamide group and an acetoxy group, an alkoxy group having 1 to 6 carbon atoms such as a methoxy group and an ethoxy group, a halogen atom such as a chlorine atom and a bromine atom, An alkoxycarbonyl group having 2 to 7 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group and a cyclohexyloxycarbonyl group, a carbonic ester group such as a cyano group and a t-butylcarbonyl group, and the like.

In the formula (S), R ³ represents a linking group of (m + n). and m + n satisfies 3 to 10.

The (m + n) linking group represented by R ³ includes 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 100 hydrogen atoms, A group formed from 20 sulfur atoms, which may be unsubstituted or may further have a substituent.

Specific examples of the (m + n) linking group include the following structural units or groups in which the structural units are combined (may form a cyclic structure).

(m + n) bond is formed from 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 40 oxygen atoms, 1 to 120 hydrogen atoms, and 0 to 10 sulfur atoms, Group is preferably a group formed from 1 to 50 carbon atoms, 0 to 10 nitrogen atoms, 0 to 30 oxygen atoms, 1 to 100 hydrogen atoms, and 0 to 7 sulfur atoms A group formed from 1 to 40 carbon atoms, 0 to 8 nitrogen atoms, 0 to 20 oxygen atoms, 1 to 80 hydrogen atoms, and 0 to 5 sulfur atoms is particularly preferable .

When the (m + n) th connecting group has a substituent, examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, an aryl group having 6 to 16 carbon atoms such as a phenyl group and a naphthyl group, , An acyloxy group having 1 to 6 carbon atoms such as a carboxyl group, a sulfonamide group, an N-sulfonylamide group and an acetoxy group, an alkoxy group having 1 to 6 carbon atoms such as a methoxy group and an ethoxy group, An alkoxycarbonyl group having 2 to 7 carbon atoms such as a halogen atom, a methoxycarbonyl group, an ethoxycarbonyl group and a cyclohexyloxycarbonyl group, and a carbonic ester group such as a cyano group and a t-butylcarbonate group.

It is preferable that the (m + n) linking group represented by R ³ is a group represented by any one of the following formulas.

Wherein,

L ³ represents a trivalent group. T ³ represents a single bond or a divalent linking group, and the three T ³ present may be the same or different.

L ⁴ represents a tetravalent group. T ⁴ represents a single bond or a divalent linking group, and the four T ⁴ present may be the same or different.

L ⁵ represents a five-valent group. T ⁵ represents a single bond or a divalent linking group, and five T ⁵ present may be the same or different.

L ⁶ represents a 6-valent group. T ⁶ represents a single bond or a divalent linking group, and the six T ⁶ present may be the same or different.

Each of L ^{3 to} L ⁶ is independently selected from the group consisting of the above-mentioned 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 40 oxygen atoms, 1 to 120 hydrogen atoms, and 0 to 10 sulfur atoms A group of trivalent to hexavalent being formed, and is preferably a group of 1 to 50 carbon atoms, 0 to 10 nitrogen atoms, 0 to 30 oxygen atoms, 1 to 100 hydrogen atoms, and 0 to 7 sulfur More preferably a trivalent to hexavalent group formed from an atom and having from 1 to 40 carbon atoms, from 0 to 8 nitrogen atoms, from 0 to 20 oxygen atoms, from 1 to 80 hydrogen atoms, Particularly preferred is a trivalent to hexavalent group formed from five sulfur atoms. Further, L ^{3 to} L ⁶ may have a substituent, and the substituent is preferably a substituent which may have the above-mentioned (m + n) linking group.

Each of T ^{3 to} T ⁶ independently represents a single bond or a single bond or a single bond or an alkylene group having 1 to 50 carbon atoms, 0 to 8 nitrogen atoms, 0 to 25 oxygen atoms, 1 to 100 hydrogen atoms, A divalent linking group formed from 10 sulfur atoms is preferable and a single bond or a divalent linking group consisting of 1 to 30 carbon atoms, 0 to 6 nitrogen atoms, 0 to 15 oxygen atoms, 1 to 50 hydrogen atoms, And a divalent linking group formed from 0 to 7 sulfur atoms are more preferable, and a single bond or a divalent linking group consisting of 1 to 10 carbon atoms, 0 to 5 nitrogen atoms, 0 to 10 oxygen atoms, Particularly preferred are divalent linking groups formed from 30 hydrogen atoms, and from 0 to 5 sulfur atoms. Further, T ^{3 to} T ⁶ may have a substituent, and the substituent is preferably a substituent which the bivalent connecting group may have.

Specific examples (specific examples (1) to (17)) of the (m + n) linking group represented by R ³ are shown below. However, the present invention is not limited to these.

Of the above specific examples, the most preferable (m + n) linking groups from the viewpoints of availability of raw materials, ease of synthesis, and solubility in various solvents are the following groups.

In the formula (S), m represents 0 to 8. m is preferably from 0.5 to 5, more preferably from 0.5 to 4, and particularly preferably from 0.5 to 3.

In the above formula (S), n represents 2 to 9. n is preferably 2 to 8, more preferably 2 to 7, and particularly preferably 3 to 6.

Further, P ² in the formula (S) represents a polymer skeleton and can be selected from a known polymer or the like depending on the purpose and the like. The number of P ² present in m in formula (S) may be the same or different. P ² is preferably a monovalent group.

Examples of the polymer chain constituting the polymer skeleton include homopolymers or copolymers of vinyl monomers, ester polymers, ether polymers, urethane polymers, amide polymers, epoxy polymers, silicone polymers, and modified products or copolymers thereof , It includes a polyether / polyurethane copolymer, a copolymer of a polymer of a polyether / vinyl monomer (any of random copolymers, block copolymers and graft copolymers, more preferably a random copolymer) ], More preferably at least one member selected from the group consisting of polymers or copolymers of vinyl monomers, ester polymers, ether polymers, urethane polymers, and modified products or copolymers thereof , Polymers or copolymers of vinyl monomers It preferred, and an acrylic resin [a (meth) polymer or copolymer of acrylic monomer] are especially preferred.

The polymer is preferably soluble in an organic solvent. The component S is preferably soluble in an organic solvent. If the affinity with the organic solvent is low, for example, the affinity with the dispersion medium becomes weak, and the adsorption layer formed by the component S on the surface of the metal oxide particle sufficient for dispersion stabilization can not be ensured.

In the present invention, the polymer skeleton in P ² may have at least one acid group, but preferably has no acid group.

Examples of the polymer having an acid group constituting the polymer skeleton include polyamide amines and salts thereof having an acid group, polycarboxylic acids and their salts, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, ) Acrylate, (meth) acrylic copolymer, naphthalenesulfonic acid formalin condensate), and polyoxyethylene alkylphosphoric acid ester, polyoxyethylene alkylamine, alkanolamine, pigment derivative and the like. Among these, a (meth) acrylic acid copolymer is preferable.

The means for introducing the acid group into the polymer skeleton is not particularly limited, and means for introducing the acid group by a vinyl monomer having an acid group, means for introducing an acid group by adding the acid group using the crosslinkable side chain, or the like can be adopted. The configuration in which the polymer skeleton is composed of the constituent unit derived from a vinyl monomer having an acid group, whereby the form in which the acid group is introduced is preferable from the viewpoint of easy control of the introduction amount of the acid group and from the viewpoint of the synthesis cost.

Here, the "acid group" is exemplified as the "acid group" in the description of A ² above, and is preferably a carboxyl group.

Examples of the vinyl monomer include, but are not limited to, (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, Acrylamides, styrenes, vinyl ethers, vinyl ketones, olefins, maleimides, (meth) acrylonitrile and vinyl monomers having an acid group.

Hereinafter, preferred examples of these vinyl monomers will be described.

Examples of the (meth) acrylic esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, (Meth) acrylate, t-butyl (meth) acrylate, amyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (Meth) acrylate, octyldodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl Hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (2-methoxyethoxy) ethyl, 3-phenoxy-2-hydroxypropyl (meth) acrylate, (Meth) acrylate, 2-chloroethyl (meth) acrylate, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl Propyl (meth) acrylate, benzyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, diethylene glycol di (meth) acrylate (Meth) acrylate, triethylene glycol monomethyl ether, (meth) acrylic acid triethylene glycol monoethyl ether, (meth) acrylic acid polyethylene glycol monomethyl ether, (meth) acrylic acid polyethylene glycol monoethyl ether, (Meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, nonylphenoxy (meth) acrylate, (Meth) acrylate, trifluorobutyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tribromophenyl Hydroxyethyl (meth) acrylate, gamma -butyrolactone-2-yl (meth) acrylate and the like.

Examples of the crotonic acid esters include butyl crotonate, hexyl crotonate, and the like.

Examples of the vinyl esters include vinyl acetate, vinyl chloroacetate, vinyl propionate, vinyl butyrate, vinyl methoxy acetate, and vinyl benzoate.

Examples of the maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.

Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.

Examples of itaconic acid diesters include dimethyl itaconate, diethyl itaconate, dibutyl itaconate, and the like.

Examples of the (meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N- (Meth) acrylamide, N, N-dimethylacetamide, N, N-butyl acrylamide, Nt- butyl (meth) acrylamide, N-cyclohexyl Acrylamide, N, N-diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-nitrophenyl acrylamide, N- (Meth) acryloylmorpholine, diacetone acrylamide, N-methylol acrylamide, N-hydroxyethyl acrylamide, vinyl (meth) acrylamide, N, (Meth) acrylamide, and the like.

Examples of the styrene include styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, hydroxystyrene, methoxystyrene, butoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene , Hydroxystyrene protected with chloromethylstyrene or a group capable of being deprotected by an acidic substance (e.g., t-butoxycarbonyl group (t-Boc)), methyl vinylbenzoate, and? have.

Examples of vinyl ethers include methyl vinyl ether, ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, octyl vinyl ether, methoxyethyl vinyl ether and phenyl vinyl Ether, and the like.

Examples of the vinyl ketones include methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.

Examples of the olefins include ethylene, propylene, isobutylene, butadiene, and isoprene.

Examples of the maleimide include maleimide, butyl maleimide, cyclohexyl maleimide, phenyl maleimide and the like.

(Meth) acrylonitrile, a vinyl-substituted heterocyclic group (e.g., vinylpyridine, N-vinylpyrrolidone, vinylcarbazole and the like), N-vinylformamide, N-vinylacetamide, Imidazole, vinylcaprolactone, and the like can also be used.

Preferable examples of these vinyl monomers include those described in Japanese Patent Application Laid-Open No. 2007-277514, paragraphs 0089 to 0094, 0096 and 0097 (corresponding to U.S. Patent Application Publication No. 2010/233595, paragraphs 0105 to 0117, and 0119 to 0120) Vinyl monomers, the contents of which are incorporated herein by reference.

In addition to the above compounds, vinyl monomers having functional groups such as urethane groups, urea groups, sulfonamide groups, phenol groups and imide groups can also be used. As the monomer having a urethane group or a urea group, for example, it is possible to suitably synthesize by using an addition reaction between an isocyanate group and a hydroxyl group or an amino group. Concretely, an addition reaction of an isocyanate group-containing monomer with a compound containing one hydroxyl group or a compound containing one primary or secondary amino group, or an addition reaction of a hydroxyl group-containing monomer or a monomer containing a primary or secondary amino group Addition reaction of monoisocyanate, and the like.

Next, a vinyl monomer having an acid group used for introducing an acid group into the polymer skeleton P ² will be described.

Examples of the vinyl monomer having an acid group include a vinyl monomer having a carboxyl group and a vinyl monomer having a sulfonic acid group.

Examples of the vinyl monomer having a carboxyl group include (meth) acrylic acid, vinylbenzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid and acrylic acid dimer. Further, an addition reaction product with a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride or cyclohexanedicarboxylic anhydride, ω-carboxypolycaprolactone mono ) Acrylate can also be used. In addition, an anhydride-containing monomer such as maleic anhydride, itaconic anhydride, or citraconic anhydride may be used as a precursor of a carboxyl group. Among these, (meth) acrylic acid is particularly preferable from the viewpoint of copolymerization, cost, solubility and the like.

As vinyl monomers having sulfonic acid group, 2-acrylamide-2-methylpropane sulfonic acid and the like can be given. As vinyl monomers having a phosphoric acid group, mono (2-acryloyloxyethyl ester) phosphate, mono (1- 2-acryloyloxyethyl ester) and the like.

As the vinyl monomer having an acid group, a vinyl monomer containing a phenolic hydroxyl group or a vinyl monomer containing a sulfonamide group may also be used.

When the polymer skeleton P ² contains a monomer unit derived from a vinyl monomer containing an acid group, the content of the vinyl monomer-derived monomer unit having an acid group in the polymer skeleton is 3% by mass to 40% by mass based on the mass of the polymer skeleton %, More preferably 5% by mass to 20% by mass.

The polymer skeleton at P ² preferably has at least a structure represented by the following formula (L), (M) or (N), and has at least a structure represented by the following formula (L) More preferable.

Wherein,

X ¹ represents a hydrogen atom or a monovalent organic group. From the viewpoint of synthesis, X ¹ is preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, more preferably a hydrogen atom or a methyl group, and particularly preferably a methyl group.

R ¹⁰ represents a hydrogen atom or a monovalent organic group, and is not particularly limited in structure, but is preferably a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group, more preferably a hydrogen atom or an alkyl group. When R ¹⁰ is an alkyl group, the alkyl group is preferably a straight chain alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 5 to 20 carbon atoms, and a straight chain alkyl group having 1 to 20 carbon atoms And a straight chain alkyl group having 1 to 6 carbon atoms is particularly preferable. In the formula (L), two or more kinds of R ¹⁰ having different structures may be contained.

R ¹¹ and R ¹² are branched or straight chain alkylene groups (preferably 1 to 10 carbon atoms, more preferably 2 to 8 carbon atoms, and more preferably 3 to 6 carbon atoms). Or two or more kinds of R ¹¹ or R ¹² having different structures may be contained in each formula.

k1, k2 and k3 each independently represent a number of 5 to 140.

The above-mentioned P ² preferably contains at least one constituent repeating unit.

The repeating number k of the at least one constituent repeating unit in the above-mentioned P ² is preferably 3 or more from the viewpoint of exhibiting a steric repulsion to improve dispersibility and achieving a high refractive index and a low viscosity, desirable.

From the viewpoint of achieving a low viscosity by suppressing the volume of the component S from being increased and also achieving a high refractive index by densely presenting the metal oxide particles in the cured film (transparent film), the The number of repeating units k is preferably 50 or less, more preferably 40 or less, and still more preferably 30 or less.

The component S is preferably soluble in an organic solvent. If the affinity with the organic solvent is high, the affinity with the dispersion medium is sufficient, and sufficient attraction force for dispersion stabilization of the metal oxide particles can be secured.

It is most preferable that R ³ , R ⁴ , R ⁵ , P ² , m and n shown below are all satisfied among the dispersants having at least one acid group represented by the above formula (S).

R ³ : The compound of the above Examples (1), (2), (10), (11), (16)

R ^{4 represents a} single bond, or a "single bond consisting of 1 to 10 carbon atoms, 0 to 5 nitrogen atoms, 0 to 10 oxygen atoms, 1 to 30 hydrogen atoms (Having 1 to 20 carbon atoms such as a methyl group, an ethyl group, an alkyl group having 1 to 20 carbon atoms, a phenyl group, a naphthyl group and the like) having 6 or more carbon atoms An alkoxy group having 1 to 6 carbon atoms such as methoxy, ethoxy and the like, such as an alkyl group having 1 to 6 carbon atoms, an aryl group having 1 to 6 carbon atoms, a hydroxyl group, an amino group, a carboxyl group, a sulfonamide group, an N-sulfonylamide group, A halogen atom such as a chlorine atom or a bromine atom, a carbonic ester group such as an alkoxycarbonyl group having 2 to 7 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group or a cyclohexyloxycarbonyl group, a cyano group or a t-butylcarbonate group, Can be)

R ^{5 is a} single bond, an ethylene group, a propylene group, a group (a) or a group (b)

In the following groups, R ¹² represents a hydrogen atom or a methyl group, and L represents 1 or 2.

P ² : a copolymer of a vinyl monomer having a carboxyl group and another vinyl monomer; Polymers or copolymers of vinyl monomers without an acid group; A polymer which is selected from the group consisting of an ester-based polymer, an ether-based polymer, a urethane-based polymer, and modified products thereof and may contain at least one acid group

m: 0.5 to 3

n: 3 to 6

The content of the acid group in the component S is appropriately determined by the acid value of the component S. The acid value of the component S is preferably 20 to 300 (mgKOH / g), more preferably 50 to 250 (mgKOH / g) and particularly preferably 50 to 210 (mgKOH / g). When the acid value is not less than 20 (mgKOH / g), the alkali developability of the photosensitive resin composition is sufficiently obtained. When the acid value is not more than 300 (mgKOH / g), the dispersibility and dispersion stability of the metal oxide particles are excellent.

Here, the acid value of the component S is the solid component acid value of the component S.

In the present invention, the acid value of component S can be calculated from the average content of acid groups in component S, for example. The acid value of the component S can be adjusted by appropriately adjusting the amount of the acid group in the component S and the amount of the above-mentioned functional group having a pKa of 5 or more. For example, when the amount of the compound having an acid group and an ethylenic unsaturated bond as raw materials and the amount of a compound having a functional group having a pKa of 5 or more and an ethylenically unsaturated bond and the amount of the vinyl monomer having an acid group The component S having a desired acid value can be synthesized.

&Lt; Synthesis method of component S >

The method of synthesizing the component S is not particularly limited. However, the method of synthesizing the component S is not particularly limited. However, in the paragraphs 0114 to 0140 and 0266 to 0348 (corresponding to U.S. Patent Application Publication No. 2010/233595, paragraphs 0145 to 0173 and 0289 To &lt; RTI ID = 0.0 &gt; 429). &Lt; / RTI &gt;

In particular, it is preferable to synthesize component S by a method of radically polymerizing a vinyl monomer in the presence of a mercaptan compound having a plurality of the adsorption sites.

The vinyl monomers may be polymerized singly or in combination of two or more.

Hereinafter, preferred specific examples (M-1) to (M-12) of the vinyl monomers are shown below, but the present invention is not limited thereto.

As a method of synthesizing the component S, more specifically, a method of radically polymerizing a vinyl monomer in the presence of a compound represented by the following formula (S ') can be preferably used.

R ⁶ , R ⁷ , A ³ , m and n in formula (S ') are the same as R ³ , R ⁴ , A ² , m and n in formula (S) The same goes for forms.

Further, as a method for synthesizing the component S, a method of adding a compound represented by the formula (S ') and a macromonomer having an ethylenic unsaturated bond (an ene-thiol reaction method) is also preferable. It is preferable to use a radical generator or a base as a catalyst for the reaction.

Specific examples of the macromonomer having an ethylenically unsaturated bond are shown below, but the present invention is not limited thereto. In the following specific examples, the number of repeating units k represents an integer of 3 to 50.

Also, as a method for synthesizing the component S, a method of forming a thioester group by a dehydration condensation reaction between the compound represented by the formula (S ') and a polymer compound having a carboxylic acid group is also preferable.

Specific examples of the polymer compound having a carboxylic acid group are shown below, but the present invention is not limited thereto. In the following specific examples, the number of repeating units k represents an integer of 3 to 50.

Also, as a method of synthesizing the component S, a method of forming a thioether group by a nucleophilic substitution reaction of a compound represented by the formula (S ') and a polymer compound having a leaving group is also preferable. As the eliminator, a sulfonate ester group such as a halogen atom such as iodine atom, bromine atom or chlorine atom, a tosylate group, a mesylate group or a trifluoromethanesulfonate group is preferable.

Specific examples of the polymer compound having a leaving group are shown below, but the present invention is not limited thereto. In the following specific examples, the number of repeating units k represents an integer of 3 to 50.

The component S is preferably synthesized by the following method.

A method of adding a compound having 3 to 10 mercapto groups in one molecule and a compound having an adsorption site and having an ethylenic unsaturated bond capable of reacting with a mercapto group

It is particularly preferable that the addition reaction is a radical addition reaction. The ethylenically unsaturated bond is more preferably a monosubstituted or disubstituted vinyl group in view of reactivity with a mercapto group.

Specific examples of the compound having three to ten mercapto groups in one molecule [specific examples (18) to (34)] include the following compounds.

Particularly preferred compounds among the above are the following compounds from the viewpoints of availability of raw materials, ease of synthesis, and solubility in various solvents.

(33) is available as a commercial product (for example, (33) is dipentaerythritol hexakis (3-mercaptopropionate) manufactured by Sakai Kagaku Kogyo Co., Ltd.).

(Specifically, a compound having an organic dye structure, a heterocyclic structure, an acid group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a saturated oxygen atom, an alkoxy A group selected from the group consisting of a silyl group, a phenol group, an alkyl group, an aryl group, an alkyleneoxy group, an imide group, an alkyloxycarbonyl group, an alkylaminocarbonyl group, a carboxylate group, a sulfonamide group, an epoxy group, an isocyanate group and a hydroxyl group A compound having at least one partial structure and having an ethylenic unsaturated bond) is not particularly limited, but the following may be mentioned.

The radical addition reaction product of the above-mentioned "compound having 3 to 10 mercapto groups in one molecule" and "compound having an adsorption site and having an ethylenic unsaturated bond" is, for example, Compound having 10 sites of mercapto group &quot; and &quot; compound having an adsorption site and having an ethylenic unsaturated bond &quot; in an appropriate solvent, and adding a radical generator to the mixture at about 50 ° C to 100 ° C (Ene-thiol reaction method).

Examples of a suitable solvent to be used in the above-mentioned enthiol reaction method include a compound having 3 to 10 mercapto groups in one molecule, a compound having an adsorption site and having an ethylenically unsaturated bond, Can be arbitrarily selected depending on the solubility of the &quot; radical addition reaction product produced &quot;.

Methoxy-2-propyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, methoxy (methoxy) propyl acetate, isopropanol, isopropanol, Propyl acetate, ethyl lactate, ethyl acetate, acetonitrile, tetrahydrofuran, dimethylformamide, chloroform, and toluene. These solvents may be used in a mixture of two or more kinds.

Examples of the radical generator include 2,2'-azobis (isobutyronitrile) (AIBN), 2,2'-azobis (2,4'-dimethylvaleronitrile) and 2,2'-azobisis Azo compounds such as dimethyl butyrate [V-601, manufactured by Wako Pure Chemical Industries, Ltd.], peroxides such as benzoyl peroxide, and persulfates such as potassium persulfate and ammonium persulfate.

The component S is preferably obtained by polymerizing these vinyl monomers and a compound represented by the formula (S ') according to a conventional method by a known method. In addition, the compound represented by the formula (S ') in the present invention functions as a chain transfer agent, and hereinafter may be simply referred to as a &quot; chain transfer agent &quot;.

For example, by dissolving the vinyl monomer and the chain transfer agent in a suitable solvent, adding a radical polymerization initiator thereto, and polymerizing the solution in a solution at about 50 ° C to 220 ° C (solution polymerization method).

Examples of a suitable solvent to be used in the solution polymerization method may be arbitrarily selected depending on the monomers to be used and the solubility of the resulting copolymer. Methoxy-2-propyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, methoxy (methoxy) propyl acetate, isopropanol, isopropanol, Propyl acetate, ethyl lactate, ethyl acetate, acetonitrile, tetrahydrofuran, dimethylformamide, chloroform, and toluene. These solvents may be used in a mixture of two or more kinds.

As the radical polymerization initiator, a known radical polymerization initiator can be used. For example, the azo compound, peroxide, persulfate, and the like can be preferably used as the radical generator.

The molecular weight of the component S is preferably 2,000 to 200,000, more preferably 2,000 to 15,000, and particularly preferably 2,500 to 10,000 in terms of weight average molecular weight. When the weight average molecular weight is within the above range, the effects of the plurality of adsorption sites introduced at the ends of the polymer are sufficiently exerted to exhibit adsorption to the solid surface.

The component S contained in the resin composition of the present invention may be one kind alone or two or more kinds. In the case of two or more types, the total is preferably in the above range.

Hereinafter, the exemplified compounds of the component S are mentioned, but the present invention is not limited thereto, and any structure may be adopted as long as it is included in the formula (S). Further, in the following example compounds, P1 and P2 may take arbitrary values in mass conversion, respectively. In the following exemplified compounds, the sulfur atom bonded to the polymer chain may be bonded to any monomer unit. The other end of the polymer chain, which is not bonded to the sulfur atom, is not shown in the following chemical formula, Lt; / RTI &gt;

Further, R ³ in (S-1-14) to (S-1-19) is the following group.

Among the exemplified compounds of the component S, the content ratio (P1: P2) of the monomer unit having a carboxylic acid ester and the monomer unit having a carboxyl group in a polymer skeleton is in the range of 100: 0 to 80:20 in terms of mass desirable.

The component S can be synthesized by referring to the method described in, for example, Japanese Patent Application Laid-Open No. 2008-96678.

The content of the component S in the photosensitive resin composition of the present invention is preferably in the range of 5 to 70 mass%, more preferably in the range of 10 to 50 mass% with respect to the total solid content of the photosensitive resin composition.

- Other dispersants -

The photosensitive resin composition of the present invention may contain a dispersant other than the component S (hereinafter sometimes referred to as &quot; other dispersant &quot;) for the purpose of adjusting the dispersibility of the metal oxide particles.

Examples of other dispersants that can be used in the present invention include known dispersants, but may include polymer dispersants other than the component S (for example, polyamide amines and salts thereof, polycarboxylic acids and their salts, high molecular weight unsaturated acid esters, (Meth) acrylic copolymer, naphthalenesulfonic acid formalin condensate], and polyoxyethylene alkylphosphoric acid ester, polyoxyethylene alkylamine, alkanolamine, pigment derivative, and the like, .

Other polymer dispersants can be further classified into linear polymers, terminal modified polymers, graft polymers, and block polymers from their structures.

Other dispersants act on the surface of the metal oxide particles to prevent re-agglomeration. Therefore, an end-modified polymer having an anchor portion to the surface of the metal oxide particle, a graft-type polymer, and a block-type polymer can be mentioned as preferable structures.

On the other hand, the other dispersant may have an effect of promoting the adsorption of the dispersed resin by modifying the surface of the metal oxide particle.

Specific examples of other polymeric dispersants include DISPERBYK 101 (polyamide amine phosphate), 107 (carboxylic acid ester), 110, 180 (copolymer containing an acid group), 130 (polyamide), 161, 162, 163 (High molecular weight unsaturated polycarboxylic acid), EFKA 4047, 4050, 4010, 4165 (polyurethane), EFKA 4330, 4340 (Block copolymer), 4400, 4402 (modified polyacrylate), 5010 (polyester amide), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative) AJISPER PB821, PB822 "manufactured by Ajinomoto Fine Techno Co., Ltd.," Floren TG-710 (urethane oligomer) "manufactured by Kyowa Ishikagaku Co., Ltd., Polyflow No. 50E, No.300 (Acrylic copolymer), Disperon KS-860, 873SN, 874 and # 2150 (manufactured by Goosumoto Kasei Co., Ltd. (aliphatic polyvalent carboxyl DA-705, DA-705, DA-725 "manufactured by Kao Corp.," Demol RN, N (naphthalenesulfonic acid formalin polycondensate) ", MS, C, SN -B (aromatic sulfonic acid formalin polycondensate) "," Homogenol L-18 (high molecular polycarboxylic acid) "," Emulsion 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether) 22000 (azo pigment derivative), 13240 (polyester amine), 3000, 17000, 27000 (polymer having functional part at the terminal part), 24000, NIKOL T106 (polyoxyethylene sorbitan monooleate) and MYS-IEX (polyoxyethylene monostearate) "available from Nikko Chemicals Co., Ltd. .

Further, as another dispersant, a compound represented by the formula (ED) after the Japanese Patent Laid-Open Publication No. 2012-208494 (paragraph 0692 of the corresponding U.S. Patent Application Publication No. 2012/235099) ) As an essential monomer component, and the contents thereof are incorporated herein by reference.

As concrete examples of the ether dimer, it is possible to consider the description of the ether dimer of Japanese Patent Application Laid-Open Publication No. 2012-208494, paragraph 0565 (corresponding to US Patent Application Publication No. 2012/235099 [0694]), Are incorporated herein by reference.

Specific examples of the polymer obtained by polymerizing a compound represented by the formula (ED) as an essential monomer component include a polymer obtained by polymerizing a compound represented by the following formula (ED) as an essential monomer component in the term of the binder polymer And the like.

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

The photosensitive resin composition of the present invention may or may not contain other dispersion resins, but if contained, the content of other dispersants relative to the total solid content of the photosensitive resin composition is preferably in the range of 1 to 20 mass%, more preferably 1 to 10 mass% % Is more preferable.

(Component B)

The photosensitive resin composition of the present invention (component B) contains a photoacid generator. As the photoacid generator (also referred to as &quot; component B &quot;) 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, It is not. Also, with respect to a photoacid generator which does not directly react with an actinic ray having a wavelength of 300 nm or more, it can be preferably used in combination with a sensitizer if the compound is used in combination with a sensitizer to generate an acid in response to an actinic ray having a wavelength of 300 nm or more. As the photoacid generator used in the present invention, a photoacid generator that generates an acid with a pKa of 4 or less is preferable, a photoacid generator that generates an acid with a pKa of 3 or less is more preferable, and a photoacid generator that generates an acid with a pKa of 2 or less desirable.

Examples of the photoacid generator include trichloromethyl-s-triazine, sulfonium salts and iodonium salts, quaternary ammonium salts, diazomethane compounds, imidosulfonate compounds and oxime sulfonate compounds . Among them, it is preferable to use an oxime sulfonate compound from the viewpoint of insulation. These photoacid generators may be used alone or in combination of two or more. Specific examples of trichloromethyl-s-triazine, diaryl iodonium salts, triarylsulfonium salts, quaternary ammonium salts and diazomethane derivatives are described in paragraphs 0083 to 0088 of Japanese Patent Laid-Open Publication No. 2011-221494 The compounds described can be exemplified.

As the oxime sulfonate compound, that is, the compound having an oxime sulfonate structure, a compound containing an oxime sulfonate structure represented by the following formula (B1) can be preferably exemplified.

(In the formula (B1), R ²¹ represents an alkyl group or an aryl group, and a broken line portion represents a bonding site with another group.

The alkyl group in R &lt; ²¹ &gt; may be linear, branched or cyclic. The permissible substituents are described below.

As the alkyl group for R ²¹ , a linear or branched alkyl group having 1 to 10 carbon atoms is preferable. The alkyl group of R ²¹ is preferably an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cycloalkyl group (including a polycyclic alicyclic group such as a 7,7-dimethyl-2-oxononyl group, An alkyl group or the like).

As the aryl group for R ^21, an aryl group having 6 to 11 carbon atoms is preferable, and a phenyl group or a naphthyl group is more preferable. The aryl group of R ²¹ may be substituted with an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom.

It is also preferable that the compound containing the oximesulfonate structure represented by the formula (B1) is an oxime sulfonate compound represented by the following formula (B2).

Wherein (B2) of, R ⁴² represents an alkyl group or an aryl group, X is an alkyl group, an alkoxy group or a halogen atom, m4 is an integer of 0 to 3, when m4 is 2 or 3, a plurality of X is Same or different]

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

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

The halogen atom as X is preferably a chlorine atom or a fluorine atom.

m4 is preferably 0 or 1. In the formula (B2), and m4 are 1, X is a methyl group, and the substitution position of X in o-position, R ⁴² is oxo norbornyl group straight chain alkyl, 7,7-dimethyl-2 of 1 to 10 carbon atoms , Or a p-toluyl group is particularly preferable.

It is also preferable that the compound containing an oxime sulfonate structure represented by the above formula (B1) is an oxime sulfonate compound represented by the following formula (B3).

Equation (B3) of, R ⁴³ is R ⁴² and agreed in the formula (B2), X ¹ is an alkoxy group of the alkyl group, having 1 to 4 carbon atoms a halogen atom, a hydroxyl group, having 1 to 4 carbon atoms, a cyano group or a nitro group And n4 represents an integer of 0 to 5,

R ⁴³ in the formula (B3) is preferably a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-octyl group, a trifluoromethyl group, a pentafluoroethyl group, a perfluoro- N-butyl group, p-tolyl group, 4-chlorophenyl group or pentafluorophenyl group is preferable, and n-octyl group is particularly preferable.

X ¹ is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group.

As n4, an integer of 0 to 2 is preferable, and 0 or 1 is particularly preferable.

Specific examples of the compound represented by the above formula (B3) include α- (methylsulfonyloxyimino) benzyl cyanide, α- (ethylsulfonyloxyimino) benzyl cyanide, α- (n-propylsulfonyloxyimino) Benzyl cyanide,? - (methylsulfonyloxyimino) -4-methoxyphenyl, benzyl cyanide,? - (n-butylsulfonyloxyimino) benzyl cyanide, - [(ethylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, alpha - [(n-propylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, n-butylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, and? - [(4-toluenesulfonyloxyimino) -4-methoxyphenyl] acetonitrile.

Specific examples of the preferable oxime sulfonate compound include the following compounds (i) to (viii), and they can be used singly or in combination of two or more kinds. The compounds (i) to (viii) are commercially available. It may also be used in combination with other types of (B) photoacid generators.

The compound containing an oxime sulfonate structure represented by the above formula (B1) is also preferably a compound represented by the following formula (OS-1).

In the formula (OS-1), R ¹⁰¹ 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, an aryl group or a heteroaryl group . R ¹⁰² represents an alkyl group or an aryl group.

¹⁰¹ X is ^{-O-, -S-, -NH-, -NR 105} -, -CH 2 -, -CR 106 H-, or -CR ¹⁰⁵ R ¹⁰⁷ - represents a, R ¹⁰⁵ ~R ¹⁰⁷ is an alkyl group, or Lt; / RTI &gt;

R ¹²¹ to R ¹²⁴ 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, an amide group, a sulfo group, a cyano group or an aryl group. Two of R ¹²¹ to R ¹²⁴ may be bonded to each other to form a ring.

As R ¹²¹ to R ¹²⁴ , a hydrogen atom, a halogen atom, or an alkyl group is preferable, and at least two of R ¹²¹ to R ¹²⁴ are bonded to each other to form an aryl group. Among them, a form in which all of R ¹²¹ to R ¹²⁴ are hydrogen atoms is preferable from the viewpoint of sensitivity.

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

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

Of the above formula (OS-2), R ¹⁰¹ , R ¹⁰² and R ¹²¹ to R ¹²⁴ are the same as those in formula (OS-1), and preferable examples are also the same.

Among these is represented by the formula (OS-1) and the expression (OS-2) R ¹⁰¹ is a cyano group, or an aryl group are more preferable due to type, and the expression (OS-2) in, R ¹⁰¹ is cyano An naphthyl group, a phenyl group or a naphthyl group is most preferable.

In the oxime sulfonate compound of the present invention, the stereostructure (E, Z, etc.) of oxime or benzothiazole ring may be either one or a mixture thereof.

Specific examples of the compounds represented by the above formula (OS-1) which can be preferably used in the present invention include compounds (exemplified compounds b-1 to b-34) described in paragraphs 0128 to 0132 of Japanese Patent Application Laid- However, the present invention is not limited to this.

In the present invention, the compound containing an oxime sulfonate structure represented by the formula (B1) is preferably a compound containing oxime sulfonate represented by the following formula (OS-3), the following formula (OS-4) It is preferably a compound of the formula (I).

In the formulas (OS-3) to (OS-5), R ²² , R ²⁵ and R ²⁸ each independently represent an alkyl group, an aryl group or a heteroaryl group, and R ²³ , R ²⁶ and R ²⁹ each independently R ²⁴ , R ²⁷ and R ³⁰ each independently represents a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group, and X ¹ to R ³⁰ each independently represent a hydrogen atom, an alkyl group, an aryl group or a halogen atom, X ³ each independently represents an oxygen atom or a sulfur atom, n ^{1 to} n ³ each independently represent 1 or 2, and m ^{1 to} m ³ each independently represent an integer of 0 to 6,

In the above formulas (OS-3) to (OS-5), the alkyl group, aryl group or heteroaryl group in R ²² , R ²⁵ and R ²⁸ may have a substituent.

Of the above-mentioned formulas (OS-3) to (OS-5), the alkyl group for R ²² , R ²⁵ and R ²⁸ is preferably an alkyl group having 1 to 30 total carbon atoms which may have a substituent.

Of the above-mentioned formulas (OS-3) to (OS-5), the aryl group in R ²² , R ²⁵ and R ²⁸ is preferably an aryl group having 6 to 30 total carbon atoms which may have a substituent.

Of the above-mentioned formulas (OS-3) to (OS-5), the heteroaryl group for R ²² , R ²⁵ and R ²⁸ is preferably a heteroaryl group having 4 to 30 total carbon atoms which may have a substituent.

Of the above-mentioned formulas (OS-3) to (OS-5), the heteroaryl group in R ²² , R ²⁵ and R ²⁸ may be at least one of the heteroaromatic rings, and for example, good.

Of the above formulas (OS-3) to (OS-5), R ²³ , R ²⁶ and R ²⁹ are preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or an alkyl group.

Of the above-mentioned formulas (OS-3) to (OS-5), one or two of R ²³ , R ²⁶ and R ²⁹ present in two or more of the compounds are preferably an alkyl group, an aryl group or a halogen atom, More preferably an alkyl group, an aryl group or a halogen atom, and it is particularly preferable that one is an alkyl group and the remainder is a hydrogen atom.

The alkyl group in R ²³ , R ²⁶ and R ²⁹ 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.

The aryl group for R ²³ , R ²⁶ and R ²⁹ is preferably an aryl group having 6 to 30 total carbon atoms which may have a substituent.

In the formulas (OS-3) to (OS-5), X ^{1 to} X ³ each independently represents O or S, and is preferably O.

In the formulas (OS-3) to (OS-5), the ring containing X ^{1 to} X ³ as a reduction is a 5-membered ring or a 6-membered ring.

In the formulas (OS-3) to (OS-5), n ^{1 to} n ³ each independently represent 1 or 2, and when X ^{1 to} X ³ are O, n ^{1 to} n ³ each independently represent 1 , And when X ^{1 to} X ³ are S, n ^{1 to} n ³ are each independently 2.

In the formulas (OS-3) to (OS-5), R ²⁴ , R ²⁷ and R ³⁰ each independently represent a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group. Among them, R ²⁴ , R ²⁷ and R ³⁰ are each independently preferably an alkyl group or an alkyloxy group.

The alkyl group, alkyloxy group, sulfonic acid group, aminosulfonyl group and alkoxysulfonyl group in R ²⁴ , R ²⁷ and R ³⁰ may have a substituent.

Of the above-mentioned formulas (OS-3) to (OS-5), the alkyl group for R ²⁴ , R ²⁷ and R ³⁰ is preferably an alkyl group having 1 to 30 total carbon atoms which may have a substituent.

Among the above-mentioned formulas (OS-3) to (OS-5), the alkyloxy group in R ²⁴ , R ²⁷ and R ³⁰ is preferably an alkyloxy group having 1 to 30 total carbon atoms which may have a substituent.

In the formulas (OS-3) to (OS-5), m ^{1 to} m ³ each independently represent an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1 , And particularly preferably 0.

(OS-3) to (OS-5) described in paragraphs 0092 to 0109 of Japanese Patent Laid-Open Publication No. 2011-221494 are added to the respective substituents of the above formulas (OS- Is also preferable.

It is particularly preferable that the compound containing an oxime sulfonate structure represented by the formula (B1) is an oxime sulfonate compound represented by any one of the following formulas (OS-6) to (OS-11).

Equation (OS-6) ~ (OS -11) of, R ³⁰¹ ~R ³⁰⁶ represents an alkyl group, an aryl group or a heteroaryl group, R ³⁰⁷ represents a hydrogen atom or a bromine atom, R ³⁰⁸ ~R ^310, R ³¹³ , R ³¹⁶ and R ³¹⁸ each independently represent 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, R ³¹¹ and R ³¹⁴ A halogen atom, a methyl group or a methoxy group, and R ³¹² , R ³¹⁵ , R ³¹⁷ and R ³¹⁹ each independently represent a hydrogen atom or a methyl group,

The preferable range of the formulas (OS-6) to (OS-11) is the same as the preferable range of (OS-6) to (OS-11) described in paragraphs 0110 to 0112 of Japanese Patent Application Laid- to be.

Specific examples of the oxime sulfonate compound represented by the above formulas (OS-3) to (OS-5) include the compounds described in paragraphs 0114 to 0120 of JP-A No. 2011-221494, Are not limited to these.

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

Component B may be used alone, or two or more kinds may be used in combination.

(Component C) Metal oxide particles

The resin composition of the present invention contains metal oxide particles for the purpose of controlling the refractive index and light transmittance. Since the metal oxide particles have high transparency and light transmittance, a positive photosensitive resin composition having high refractive index and excellent transparency can be obtained.

The component C preferably has a refractive index higher than that of the resin composition made of a material other than the above-mentioned particles, more specifically, particles having a refractive index of 1.50 or more in a light having a wavelength of 400 to 750 nm, more preferably a refractive index of 1.70 Or more, more preferably 1.90 or more. Further, particles having a refractive index of 2.80 or less are preferable.

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

In addition, the metal of the metal oxide particle in the present invention includes a semi-metal such as B, Si, Ge, As, Sb and Te.

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

From the viewpoint of transparency of the resin composition, the average primary particle diameter of the component C is preferably from 1 to 200 nm, particularly preferably from 3 to 80 nm. Here, the average primary particle diameter of the particles refers to the arithmetic mean of 200 particle diameters of arbitrary particles measured by an electron microscope. When the shape of the particles is not spherical, the maximum diameter is defined as the particle diameter.

Component C may be used singly or in combination of two or more.

The content of the metal oxide particles in the resin composition of the present invention may be suitably determined in consideration of the refractive index and light transmittance required for the optical member obtained by the resin composition, By mass to 80% by mass, and more preferably from 10 to 70% by mass.

(Component D) Solvent

The photosensitive resin composition of the present invention contains (Component D) a solvent. It is preferable that the photosensitive resin composition of the present invention is prepared as a solution in which the essential component of the present invention and any of the following components are dissolved in the (D) solvent.

As the solvent used in the photosensitive resin composition of the present invention, a known solvent can be used, and examples thereof include ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol Propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol mono Alkyl ether acetates, esters, ketones, amides, lactones, and the like. Specific examples of the solvent to be used in the photosensitive resin composition of the present invention include the solvents described in paragraphs 0174 to 0178 of Japanese Patent Laid-Open Publication No. 2011-221494.

In these solvents, if necessary, benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, caproic acid, caprylic acid, Benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate, propylene carbonate and the like may be further added.

These solvents may be used alone or in combination of two or more. The solvent which can be used in the present invention is preferably a single solvent or a combination of two solvents.

The component D is preferably a solvent having a boiling point of 130 ° C or more and less than 160 ° C, a solvent having a boiling point of 160 ° C or more, or a mixture thereof.

Propylene glycol monomethyl ether acetate (boiling point: 146 占 폚), propylene glycol monoethyl ether acetate (boiling point: 158 占 폚), propylene glycol methyl n-butyl ether (boiling point: 155 占 폚), propylene glycol Methyl-n-propyl ether (boiling point 131 占 폚).

As the solvent having a boiling point of 160 캜 or more, ethyl 3-ethoxypropionate (boiling point: 170 캜), diethylene glycol methyl ethyl ether (boiling point: 176 캜), propylene glycol monomethyl ether propionate (boiling point: 160 캜), dipropylene glycol methyl ether acetate (Boiling point: 213 占 폚), 3-methoxybutyl ether acetate having a boiling point of 171 占 폚, diethylene glycol diethyl ether having a boiling point of 189 占 폚, diethylene glycol dimethyl ether having a boiling point of 162 占 폚, propylene glycol diacetate having a boiling point of 190 占), Diethylene glycol monoethyl ether acetate (boiling point 220 占 폚), dipropylene glycol dimethyl ether (boiling point 175 占 폚), and 1,3-butylene glycol diacetate (boiling point 232 占 폚).

Of these solvents, propylene glycol monoalkyl ether acetates are preferable, and propylene glycol monomethyl ether acetate is particularly preferable.

The content of the (component D) solvent in the photosensitive resin composition of the present invention is preferably 50 to 95 parts by mass, more preferably 60 to 90 parts by mass, per 100 parts by mass of the component A in the photosensitive resin composition.

(Component E) 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.

The crosslinking agent is not limited as long as it causes crosslinking reaction by heat (except for component A). For example, a compound having two or more epoxy groups or oxetanyl groups in the molecule, an alkoxymethyl group-containing cross-linking agent, a compound having at least one ethylenically unsaturated double bond, or a block isocyanate compound may be added, .

The addition amount of the crosslinking agent in the photosensitive resin composition of the present invention is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass relative to 100 parts by mass of the total solid content of the photosensitive resin composition desirable. When added in this range, a cured film excellent in mechanical strength and solvent resistance can be obtained. A plurality of crosslinking agents may be used together, and in that case, the total amount of the crosslinking agents is to be calculated.

&Lt; Compounds 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. For example, commercially available products such as JER157S70 and JER157S65 (manufactured by Mitsubishi Chemical Corporation), and those described in paragraph 0189 of Japanese Patent Application Laid-Open Publication No. 2011-221494.

In addition, ADEKA RESIN EP-4000S, EP-4003S, EP-4010S and EP-4011S (manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD- EX-611, EX-614B, EX-622, EX-512, EX-521, EX-411, EX EX-821, EX-821, EX-821, EX-821, EX-821, DLC-203, DLC-203, EX-841, EX-911, EX-941, EX-920, EX- YH-300, YH-301, YH-302, YH-315, YH-324 and DLC-402 (manufactured by Nagase ChemteX Corporation) YH-325 [manufactured by Shinnitetsu Kagaku Co., Ltd.], and the like.

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

Among them, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol novolak type epoxy resin and an aliphatic epoxy resin are more preferable, and a bisphenol A type epoxy resin is particularly 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 (manufactured by Doago Kosai Co., Ltd.) can be used.

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

As the other crosslinking agent, the alkoxymethyl group-containing crosslinking agent and the compound having at least one ethylenically unsaturated double bond described in paragraphs 0107 to 0108 of Japanese Patent Application Laid-Open Publication No. 2012-8223 may be preferably used. As the alkoxymethyl group-containing crosslinking agent, alkoxymethylated glycoluril is preferable.

&Lt; Block isocyanate compound >

In the photosensitive resin composition of the present invention, a block isocyanate compound can also be preferably employed as a crosslinking agent. The block isocyanate compound is not particularly limited as long as it is a compound having a block isocyanate group, but is preferably a compound having two or more block isocyanate groups in one molecule from the viewpoint of curability.

In addition, the block isocyanate group in the present invention is a group capable of forming an isocyanate group by heat, and for example, a group in which an isocyanate group is protected by reacting a blocking agent with an isocyanate group can be preferably exemplified. The block isocyanate group is preferably a group capable of generating an isocyanate group by heat at 90 to 250 캜.

The skeleton of the block isocyanate compound is not particularly limited, and any skeleton may be used as long as it has two isocyanate groups in one molecule. The skeleton may be an aliphatic, alicyclic or aromatic polyisocyanate. For example, 2,4- 1,6-hexamethylene diisocyanate, 1,3-trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, 2,2,4-trimethylhexyl isocyanate, Hexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,9-nonamethylene diisocyanate, 1,10-decamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 2,2'-di Ethyl ether diisocyanate, diphenylmethane-4,4'-diisocyanate, o-xylene diisocyanate, m-xylene diisocyanate, p- Cyclohexane-1,3-dimethylene diisocyanate, cyclohexane-1,4-dimethylene diisocyanate, 1,5-naphthalene diisocyanate, p-phenylenediisocyanate, 3-methylene diisocyanate, , 3'-methyleneditholylene-4,4'-diisocyanate, 4,4'-diphenylether diisocyanate, tetrachlorophenylenediisocyanate, norbornadiisocyanate, hydrogenated 1,3- xylylene diisocyanate, Xylylene diisocyanate and the like, and compounds having a skeleton of a prepolymer type derived from these compounds can be preferably used. Among them, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI) and isophorone diisocyanate (IPDI) are particularly preferable.

Examples of the parent structure of the block isocyanate compound in the photosensitive resin composition of the present invention include a burette type, an isocyanurate type, an adduct type, and a bifunctional prepolymer type.

Examples of the block agent forming the block structure of the block isocyanate compound include an oxime compound, a lactam compound, a phenol compound, an alcohol compound, an amine compound, an active methylene compound, a pyrazole compound, a mercaptan compound, an imidazole compound, . Among them, a block agent selected from an oxime compound, a lactam compound, a phenol compound, an alcohol compound, an amine compound, an active methylene compound, and a pyrazole compound is particularly preferable.

Examples of the oxime compounds include aldoxime and ketoxime. Specific examples thereof include acetoxime, formaldehyde, cyclohexane oxime, methyl ethyl ketone oxime, cyclohexanone oxime, benzophenone oxime, acetoxime and the like .

Examples of the lactam compound include ε-caprolactam, γ-butyrolactam, and the like.

Examples of the phenol compound include phenol, naphthol, cresol, xylenol, halogen-substituted phenol, and the like.

Examples of the alcohol compound include methanol, ethanol, propanol, butanol, cyclohexanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, and alkyl lactate.

Examples of the amine compound include a primary amine and a secondary amine, and may be an aromatic amine, an aliphatic amine, or an alicyclic amine, and examples thereof include aniline, diphenylamine, ethyleneimine, and polyethyleneimine.

Examples of the active methylene compound include diethyl malonate, dimethyl malonate, ethyl acetoacetate, and methyl acetoacetate.

Examples of the pyrazole compound include pyrazole, methylpyrazole, dimethylpyrazole and the like.

Examples of the mercaptan compound include alkyl mercaptans, aryl mercaptans, and the like.

The block isocyanate compound which can be used in the photosensitive resin composition of the present invention is available as a commercially available product, and examples thereof include Coronate AP Stable M, Coronate 2503, 2515, 2507, 2513, 2555, Millionate MS- B-812N, B-820NSU, B-842N, B-846N, B-870N, B-874N and B-882N [manufactured by Nippon Polyurethane Kogyo Co., Ltd.], Takenate B- B60, MF-B60B, MF-K60X, MF-K60B, E402-B80B, SBN-70D, SBB-60DX, TPA-B80X, 70P, K6000 (manufactured by Asahi Kasei Chemical Co., Ltd.), Desmodule BL1100, BL1265 MPA / X, BL3575 / 1, BL3272MPA, BL3370MPA, BL3475BA / SN, BL5375MPA, VPLS2078 / 2, BL4265SN, PL340, PL350, , And BL3175 (manufactured by Sumika Bayer Urethane Co., Ltd.).

(Component F) Antioxidant

The photosensitive resin composition of the present invention preferably contains an antioxidant. As the antioxidant, a known antioxidant may be contained. By adding an antioxidant, coloring 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, amides, hydrazides, hindered amine antioxidants, sulfur antioxidants, phenol antioxidants, ascorbic acids, zinc sulfate, sugars, nitrite, sulfite, thiosulfate , Hydroxylamine derivatives, and the like. Among these, phenol-based antioxidants, amide-based antioxidants, hydrazide-based antioxidants and sulfur-based antioxidants are particularly preferable from the viewpoint of coloring of a cured film and reduction of film thickness. These may be used singly or in combination of two or more kinds.

Examples of commercially available products of phenolic antioxidants include Adekastab AO-15, Adekastube AO-18, Adekastube AO-20, Adekastube AO-23, Adekastube AO-30, Adekastube AO- 60, Adeka Stove AO-70, Adeka Stove AO-80, Adeka Stove AO-50, Adeka Stove AO-60, Adeka Stove AO- 330, ADEKA STUB AO-412S, ADEKA STUB AO-503, ADEKA STUB A-611, ADEKA STUB A-612, ADEKA STUB A-613, ADEKA STUB PEP-4C, ADEKA STUB PEP-8 , Adeka Stove PEP-8W, Adeka Stove PEP-24G, Adeka Stove PEP-36, Adeka Stove PEP-36Z, Adeka Stub HP-10, Adeka Stub 2112, Adeka Stab 260, Adeka Stab 522A Adeka Stove CDA-1, Adeka Stave CDA-6, Adeka Stove CDA-1, Adeka Stave CDA-1, Adeka Stave CDA-1, Adeka Stave CDA- (Manufactured by ADEKA Co., Ltd.), Igaronx 245FF, Igaronx 1010FF, Igarazx 1010, Igaraxx MD1024, Igaracox ZS-90, Adekastab ZS-90 (Manufactured by BASF), Tinuvin 405 (manufactured by BASF), and the like can be given as examples of the composition of the present invention. Of these, Adekastab AO-60, Adekastab AO-80, Igarox 1726, Igarox 1035, Igarox 1098, and Tinuvin 405 can be preferably used.

The content of the antioxidant is preferably from 0.1 to 10 mass%, more preferably from 0.2 to 5 mass%, and particularly preferably from 0.5 to 4 mass%, based on the total solid content of the photosensitive resin composition. With this range, sufficient transparency of the film formed can be obtained, and sensitivity at the time of pattern formation becomes good.

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

<Other ingredients>

In the photosensitive resin composition of the present invention, a sensitizer, (component H) alkoxysilane compound, (component I) basic compound and (component J) surfactant may be added as needed in addition to the above components have. The photosensitive resin composition of the present invention may further contain known additives such as ultraviolet absorber, metal deactivator, acid proliferator, development promoter, plasticizer, thermal radical generator, thermal acid generator, thickener, Can be added.

(Component G) sensitizer

It is preferable that the photosensitive resin composition of the present invention contains a sensitizer for accelerating the decomposition of the component (B) in combination with the photoacid generator. 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 photoacid generator to generate electron transfer, energy transfer, heat generation, and the like. Accordingly, the photoacid generator decomposes by chemical change to generate an acid. Examples of preferred sensitizers include compounds having an absorption wavelength in any one of the wavelength ranges 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- Xanthone, xanthone, thioxanthone, dimethylthioxanthone, diethylthioxanthone, and the like), xanthone (for example, Oxanols, thiazides, thiocarbamates, thiocarbamates, thiocarbamates, thiocarbamates, thiocarbamates, thiocarbamates, thiocarbamates, (Such as acridine orange, chloroflavin, acriflavine), acridones (such as acridone, acridine, acridine), acridine (for example, thionine, methylene blue, toluidine blue) Butyl-2-chloroacridone), anthraquinones (for example, anthraquinone), squaryliums (for example, squalium), styryls, (Such as 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 [1] benzopyran [6,7,8-ij] quinolizine-11-pne).

Of these sensitizers, polynuclear aromatic compounds, acridones, styryls, base styryls and coumarins are preferable, and polynuclear aromatic compounds are more preferable. Of the polynuclear aromatics, anthracene derivatives are most preferred.

The amount of the sensitizer added to the photosensitive resin composition of the present invention is preferably 0 to 1,000 parts by mass, more preferably 10 to 500 parts by mass, more preferably 50 to 200 parts by mass relative to 100 parts by mass of the photoacid generator of the photosensitive resin composition Is more preferable.

The sensitizers may be used singly or in combination of two or more.

(Component H) The alkoxysilane compound

The photosensitive resin composition of the present invention may contain (Component H) an alkoxysilane compound. When the alkoxysilane compound is used, the adhesion between the film formed by the photosensitive resin composition of the present invention and the substrate can be improved, or the properties of the film formed by the photosensitive resin composition of the present invention can be adjusted. The alkoxysilane compound (Component H) that can be used in the photosensitive resin composition of the present invention is an alkoxysilane compound that can be used as an inorganic substance such as silicon, silicon oxide, silicon nitride such as silicon nitride, gold, copper, molybdenum, titanium, And is preferably a compound that improves the adhesion of the insulating film. Specifically, known silane coupling agents and the like are also effective.

Examples of the silane coupling agent include? -Aminopropyltrimethoxysilane,? -Aminopropyltriethoxysilane,? -Glycidoxypropyltrialkoxysilane,? -Glycidoxypropylalkyldialkoxysilane,? -Methacrylate, (3,4-epoxycyclohexyl) ethyltrialkoxysilane,? - (3,4-epoxycyclohexyl) ethyltrialkoxysilane,? -Methacryloxypropyltrialkoxysilane,? -Mercaptopropyltrialkoxysilane, , And vinyltrialkoxysilane. Among these,? -Glycidoxypropyltrialkoxysilane and? -Methacryloxypropyltrialkoxysilane are more preferable, and? -Glycidoxypropyltrialkoxysilane is even more preferable, and 3-glycidoxypropyltrimethoxy Silane is particularly preferred. These may be used singly or in combination of two or more.

The following compounds can also be preferably employed. Ph represents a phenyl group.

The alkoxysilane compound in the photosensitive resin composition of the present invention is not particularly limited to these, and known alkoxysilane compounds may be used.

The content of the alkoxysilane compound in the photosensitive resin composition of the present invention is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, per 100 parts by mass of the total solid content in the photosensitive composition.

(Component I) The basic compound

The photosensitive resin composition of the present invention may contain (Component I) a basic compound. (Component I) As the basic compound, any one selected from those used in the chemical amplification resistor can be used. Examples thereof include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, quaternary ammonium salts of carboxylic acids, and the like. Specific examples of these compounds include the compounds described in paragraphs 0204 to 0207 of Japanese Patent Laid-Open Publication No. 2011-221494.

Specific examples of the aliphatic amine include aliphatic amines such as trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di- Ethanolamine, triethanolamine, dicyclohexylamine, dicyclohexylmethylamine, and the like.

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

Examples of the heterocyclic amine include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl- Benzimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinic acid amide, quinoline, 8-oxy N-cyclohexyl-N '- [2- (4-morpholinyl) pyrimidine, Ethyl] thiourea, 1,5-diazabicyclo [4.3.0] -5-nonene, and 1,8-diazabicyclo [5.3.0] -7-undecene.

Examples of quaternary ammonium hydroxides include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide and tetra-n-hexylammonium hydroxide .

Examples of the quaternary ammonium salt of carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate and tetra-n-butylammonium benzoate.

The basic compounds usable in the present invention may be used singly or in combination of two or more kinds.

The content of the basic compound in the photosensitive resin composition of the present invention is preferably 0.001 to 3 parts by mass, more preferably 0.005 to 1 part by mass based on 100 parts by mass of the total solid content in the photosensitive resin composition.

(Component J) Surfactant

The photosensitive resin composition of the present invention may contain (component J) a surfactant.

(Component J) 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, silicones, and fluorine surfactants. (Manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), F-top (manufactured by JEMCO), Megapack (manufactured by DIC Corporation) (Manufactured by Asahi Glass Co., Ltd.), PolyFox (manufactured by OMNOVA), and SH-8400 (manufactured by Toray Dow Corning Co., Ltd.) .

The weight ratio in terms of polystyrene measured by gel permeation chromatography when the surfactant contains the constituent unit A and the constituent unit B represented by the following formula (J-1) and tetrahydrofuran (THF) A preferred example is a copolymer having an average molecular weight (Mw) of 1,000 or more and 10,000 or less.

: Wherein R ⁴⁰¹ and R ⁴⁰³ each independently represents a hydrogen atom or a methyl group; R ⁴⁰² represents a straight chain alkylene group having 1 to 4 carbon atoms and R ⁴⁰⁴ represents a hydrogen atom or a C1-4 alkyl group having 1 to 4 carbon atoms; P represents an alkylene group having 3 to 6 carbon atoms, p and q represent a percentage of mass indicating a polymerization ratio, p represents a value of 10 mass% or more and 80 mass% or less, q represents a mass of 20 mass % Or more and 90 mass% or less, r is an integer of 1 or more and 18 or less, and s is an integer of 1 or more and 10 or less,

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

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

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

The amount of the surfactant added to the photosensitive resin composition of the present invention is preferably 10 parts by mass or less, more preferably 0.001 parts by mass to 10 parts by mass, and even more preferably 0.01 parts by mass to 3 parts by mass relative to 100 parts by mass of the total solid content in the photosensitive resin composition desirable.

(Component K)

The photosensitive resin composition of the present invention can use an acid growth agent for the purpose of improving the sensitivity.

The acid-proliferating agent which can be used in the present invention is a compound capable of increasing the acid concentration in the reaction system by further generating an acid by an acid catalytic reaction, 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 are elongated by a single reaction. However, since the produced acid itself undergoes self-decomposition, the strength of the acid generated here is the acid- The pKa is preferably 3 or less, and particularly preferably 2 or less. The pKa is preferably -15 or more.

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

Examples of the acid growth agent usable in the present invention include acids having a pKa of 3 or less such as dichloroacetic acid, trichloroacetic acid, methanesulfonic acid, benzenesulfonic acid, trifluoromethanesulfonic acid and phenylphosphonic acid, which are decomposed by an acid generated from an acid generator . &Lt; / RTI &gt;

Specifically, the following compounds and the like can be mentioned.

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

(Component L) Development accelerator

The photosensitive resin composition of the present invention may contain 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 carboxyl group, a phenolic hydroxyl group, and an alkyleneoxy group, and a carboxyl group or a phenolic hydroxyl group Is more preferable, and a compound having a phenolic hydroxyl group is most preferable.

As the phenomenon promoting agent, the description of paragraphs 0171 to 0172 of Japanese Patent Application Laid-Open Publication No. 2012-042837 may be taken into consideration, and the contents thereof are incorporated herein by reference.

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

The addition amount of the development accelerator in the photosensitive resin composition of the present invention is preferably from 0 to 30 parts by mass, more preferably from 0.1 to 20 parts by mass, relative to 100 parts by mass of the total solid content of the photosensitive composition, from the viewpoints of sensitivity and remaining ratio of the unexposed portion And most preferably 0.5 to 10 parts by mass.

As the other additives, the heat radical generator described in paragraphs 0120 to 0121 of Japanese Patent Application Laid-Open Publication No. 2012-8223, the nitrogen containing compound described in International Publication No. 2011/136074 and thermal acid generation system can be used.

(Production method of cured film)

Next, a method for producing the cured film (resin pattern) of the present invention will be described.

The method for producing the cured film of the present invention preferably includes the following steps (1) to (5).

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

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

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

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

(5) A heat treatment step for heat-treating the developed resin composition.

Each step will be described below in order.

(1), it is preferable that the photosensitive resin composition of the present invention is applied onto a substrate to form a wet film containing a solvent. It is preferable to clean the substrate such as alkali washing or plasma cleaning before applying the photosensitive resin composition to the substrate, and it is more preferable to further treat the substrate surface with hexamethyldisilazane after the substrate cleaning. By this treatment, the adhesion of the photosensitive resin composition to the substrate is improved. The method of treating the surface of the substrate with hexamethyldisilazane is not particularly limited, and for example, a method of exposing the substrate to hexamethyldisilazane vapor may be mentioned.

Examples of the substrate include plastic substrates such as inorganic substrates, resins, resin composite materials, ITO, Cu substrates, polyethylene terephthalate, and cellulose triacetate (TAC).

Examples of the inorganic substrate include glass, quartz, silicon, silicon nitride, and composite substrates obtained by depositing molybdenum, titanium, aluminum, copper, or the like on a substrate such as glass, quartz, silicon or silicon nitride.

Examples of the resin include polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, polysulfone, polyether sulfone, polyarylate, allyldiglycol carbonate, polyamide, polyimide, polyamide Acrylic resin, epoxy resin, silicone resin, ionomer resin, polyimide resin, polyimide resin, polyimide resin, polyimide resin, A substrate made of a synthetic resin such as a cyanate resin, a crosslinked fumaric acid diester resin, a cyclic polyolefin, an aromatic ether resin, a maleimide-olefin resin, a cellulose, and an episulfide resin.

These substrates are rarely used in the above-described form, and a multilayer laminate structure such as a TFT device is usually formed depending on the shape of the final product.

The method of applying the coating liquid to the substrate is not particularly limited and slit coating, spraying, roll coating, spin coating, spin coating, slit-and-spin coating, and the like can be used. It is also possible to apply the so-called pre-wet method as described in JP-A-2009-145395.

The thickness of the coating film is not particularly limited, and it can be applied with a film thickness according to the application, but it is preferably used in the range of 0.5 to 10 mu m.

In the solvent removal step (2), the solvent is removed from the applied film by depressurization (vacuum pressure) and / or heating to form a dry film on the substrate. The heating condition of the solvent removing step is preferably about 70 to 130 占 폚 for 30 to 300 seconds. When the temperature and the time are in the above range, the adhesion of the pattern is good and the residue can also be reduced.

In the exposure step of the step (3), the substrate provided with a coating film is irradiated with an actinic ray through a mask having a predetermined pattern. In this process, the photoacid generator is decomposed to generate acid. By the catalytic action of the generated acid, the acid decomposable group contained in the coating film component is hydrolyzed to generate an acid group, for example, a carboxyl group or a phenolic hydroxyl group.

(436 nm), i-line (365 nm), h-line (405 nm), and the like can be used as the exposure light source by the actinic light ray. Examples of the exposure light source include a low pressure mercury lamp, a high pressure mercury lamp, Nm) or the like having a wavelength of 300 nm or more and 450 nm or less can be preferably used. If necessary, the irradiation light may be adjusted by passing through a spectral filter such as a long wavelength cutoff filter, a short wavelength cutoff filter, or a bandpass filter.

As the exposure apparatus, various types of exposure apparatus such as a mirror projection aligner, a stepper, a scanner, a proximity, a contact, a microlens array, and a laser exposure can be used.

Post-exposure heat treatment: Post Exposure Bake (hereinafter, also referred to as &quot; PEB &quot;) may be performed to accelerate the hydrolysis reaction in the region where the acid catalyst is generated. PEB can promote the generation of a carboxyl group or a phenolic hydroxyl group from an acid-decomposable group. The temperature at which PEB is carried out is preferably 30 占 폚 to 130 占 폚, more preferably 40 占 폚 to 110 占 폚, and particularly preferably 50 占 폚 to 100 占 폚.

However, since the acid decomposable group in the present invention is low in the activation energy of the acid decomposition and is easily decomposed by an acid derived from an acid generator by exposure to generate an acid group, for example, a carboxyl group or a phenolic hydroxyl group, It is possible to form a positive image by development without performing the above process.

In the developing step of (4), the liberated copolymer having a carboxyl group or a phenolic hydroxyl group is developed using an alkaline developer. A positive image is formed by removing the exposed region including a resin composition having an acid group easily soluble in an alkaline developer, for example, a carboxyl group or a phenolic hydroxyl group.

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

As a preferable developing solution, a 0.4 mass% aqueous solution, 0.5 mass% aqueous solution, 0.7 mass% aqueous solution, or 2.38 mass% aqueous solution of tetraethylammonium hydroxide can be mentioned.

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

The developing time is preferably 30 to 500 seconds, and the developing method may be any of a liquid filling method and a dipping method. After the development, washing with water for 30 to 300 seconds is carried out to form a desired pattern.

After the development, a rinsing process may be performed. In the rinsing step, the developed substrate is cleaned with pure water or the like to remove the attached developing solution and remove the developing residue. As the rinsing method, known methods can be used. Examples thereof include shower rinses and deep rinses.

In the heat treatment step (post-baking) of the substrate 5, the obtained positive image is thermally decomposed by thermal decomposition of the acid-decomposable group to form an acid group, for example, a carboxyl group or a phenolic hydroxyl group, and crosslinked with a crosslinkable group or a crosslinking agent. The heating is carried out at a predetermined temperature, for example, 180 to 250 DEG C for a predetermined time, for example, 5 to 90 minutes for a hot plate or 30 to 120 minutes for an oven using a heating apparatus such as a hot plate or an oven A protective film or an interlayer insulating film excellent in heat resistance, hardness and the like can be formed by carrying out a crosslinking reaction in which the treatment is preferably carried out. Further, when the heat treatment is performed, transparency can be improved by performing the heat treatment in a nitrogen atmosphere. When a plastic substrate is used, it is preferable to carry out the heat treatment at 80 to 140 占 폚 for 5 to 120 minutes.

Before the heat treatment process (post-baking), the heat treatment process may be performed after baking at a relatively low temperature (addition of the middle baking process). In the case of performing the middle baking, post-baking is preferably performed at a high temperature of 200 DEG C or higher after heating at 90 to 150 DEG C for 1 to 60 minutes. In addition, middle baking and post baking may be divided into three or more stages and heated. The taper angle of the pattern can be adjusted by devising such middle baking and post baking. For these heating, a known heating method such as a hot plate, an oven, and an infrared heater can be used.

As a catalyst for promoting the crosslinking step by generating an acid from the photoacid generator present in the unexposed portion by post-exposure (post exposure) to the substrate on which the pattern is formed before the post-baking, And can accelerate the curing reaction of the film. When the post exposure step is included, the preferable exposure amount is preferably 100 to 3,000 mJ / cm2, and particularly preferably 100 to 500 mJ / cm2.

The cured film obtained from the photosensitive resin composition of the present invention may also be used as a dry etching resist. When a cured film obtained by thermal curing by a heat treatment process is used as a dry etching resist, dry etching treatment such as ashing, plasma etching, and ozone etching can be performed as the etching treatment.

(Cured film)

The cured film of the present invention is a cured film obtained by curing the photosensitive resin composition of the present invention.

The cured film of the present invention can be preferably used as an interlayer insulating film. It is preferable that the cured film of the present invention is a cured film obtained by the method of forming a cured film of the present invention.

With the photosensitive resin composition of the present invention, an interlayer insulating film having excellent transparency can be obtained even when the insulating resin is baked at a high temperature. The interlayer insulating film formed using the photosensitive resin composition of the present invention is useful for an organic EL display device, a liquid crystal display device, and a touch panel display device because it has high transparency and excellent physical properties of a cured film.

(Cured product and method for producing the same)

The cured product of the present invention is a cured product obtained by curing the photosensitive resin composition of the present invention. As described above, the shape of the cured product may not be a film, and any shape may be used.

The method for producing the cured product of the present invention is not particularly limited, but preferably includes at least the following steps (a) to (c) in this order.

(a) an application step of applying the photosensitive resin composition of the present invention onto a substrate;

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

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

The steps (a) and (b) are in agreement with the coating step and the solvent removing step, respectively, and the preferred embodiments are also the same.

The step (c) is a step similar to the above-mentioned heat treatment step, except that the subject to be heat treated is the resin composition from which the solvent obtained in the step (b) has been removed. In the heat treatment step, the preferable heating temperature, heating time, The form is likewise preferred.

The cured product or the cured film of the present invention can be preferably used as an optical member such as a microlens, an optical waveguide, an antireflection film, a sealing material for LED, a chip coating material for LED, or a cured product for reducing visibility of wiring electrodes used for a touch panel have.

Further, the cured product or the cured film of the present invention can be used as a flattening film or an interlayer insulating film in a liquid crystal display device or an organic EL device or the like, a protective film of a color filter, a liquid crystal display device, A spacer for maintaining a constant shape, a structural member of a MEMS (Micro Electro Mechanical Systems) device, and the like.

(Liquid crystal display device)

The liquid crystal display device of the present invention is characterized by comprising the cured film of the present invention.

The liquid crystal display of the present invention is not particularly limited, except that it has a planarizing film or an interlayer insulating film formed by using the photosensitive resin composition of the present invention, and may be a known liquid crystal display device employing various structures.

For example, specific examples of a TFT (Thin-Film Transistor) included in the liquid crystal display of the present invention include an amorphous silicon-TFT, a low-temperature polysilicon-TFT, and an oxide semiconductor TFT. Since the cured film of the present invention is excellent in electric characteristics, it can be preferably used in combination with these TFTs.

As a liquid crystal driving method that can be employed in the liquid crystal display of the present invention, a TN (Twisted Nematic) method, VA (Virtical Alignment) method, IPS (In-Place-Switching) method, FFS , An OCB (Optical Compensated Bend) method, and the like.

In the panel construction, the cured film of the present invention can also be used in a COA (Color Filter on All) system liquid crystal display device. For example, the organic insulating film 115 described in Japanese Patent Application Laid-Open No. 2005-284291, And can be used as the organic insulating film 212 described in JP-A-346054.

Specific examples of the alignment method of the liquid crystal alignment film that can be employed in the liquid crystal display of the present invention include a rubbing alignment method and a photo alignment method. It may also be polymer-oriented supported by PSA (Polymer Sustained Aligment) technology described in Japanese Patent Laid-Open Nos. 2003-149647 and 2011-257734.

Further, the photosensitive resin composition of the present invention and the cured film of the present invention are not limited to the above-mentioned use, and can be used for various purposes. For example, in addition to a planarizing film and an interlayer insulating film, a protective film for a color filter, a spacer for keeping the thickness of the liquid crystal layer in the liquid crystal display device constant, and a microlens provided on the color filter in the solid- Can be used.

Fig. 1 is a conceptual cross-sectional view showing an example of an active matrix type liquid crystal display device 10. Fig. 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 is composed of a TFT corresponding to all the pixels arranged between two glass substrates 14, (16) are disposed on the substrate. An ITO transparent electrode 19 for passing through the contact hole 18 formed in the cured film 17 and forming the pixel electrode is wired to each element formed on the glass substrate. On the ITO transparent electrode 19, an RGB color filter 22 in which a layer of a liquid crystal 20 and a black matrix are arranged is provided.

The light source of the backlight is not particularly limited, and a known light source can be used. For example, white LEDs, multicolor LEDs such as blue, red, and green, fluorescent lamps (cold cathode tubes), and organic ELs.

Further, the liquid crystal display device may be 3D (stereoscopic) type or may be a touch panel type. The second inter-phase insulating film 48 described in JP-A-2011-145686 or the inter-phase insulating film 520 described in JP-A-2009-258758 can be used.

(Organic EL display device)

The organic EL display device of the present invention is characterized by comprising the cured film of the present invention.

The organic EL display device of the present invention is not particularly limited, except that it has a planarizing film or an interlayer insulating film formed by using the photosensitive resin composition of the present invention, and various known organic EL display devices employing various structures, liquid crystal display Devices.

For example, specific examples of a TFT (Thin-Film Transistor) included in the organic EL display device of the present invention include an amorphous silicon-TFT, a low-temperature polysilicon TFT, and an oxide semiconductor TFT. Since the cured film of the present invention is excellent in electric characteristics, it can be preferably used in combination with these TFTs.

2 is a conceptual diagram showing an example of an organic EL display device. Sectional schematic 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 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 . The wiring 2 is for connecting the organic EL element formed between the TFTs 1 or a later step to the TFT 1. [

The planarization layer 4 is formed on the insulating film 3 so as to fill the irregularities formed by the wirings 2 in order to planarize the irregularities formed by the formation of the wirings 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 flattening 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 this insulating film 8, a short circuit is prevented between the first electrode 5 and the second electrode formed in the subsequent steps can do.

Although not shown in FIG. 2, a hole transport layer, an organic light emitting layer, and an electron transport layer are sequentially deposited by a desired pattern mask, then a second electrode made of Al is formed on the entire upper surface of the substrate, It is possible to obtain an active matrix type organic EL display device in which an organic EL element is sealed by bonding using an ultraviolet curable epoxy resin and a TFT 1 for driving each organic EL element is connected.

Since the photosensitive resin composition of the present invention is excellent in curability and cured film properties, a resist pattern formed by using the photosensitive resin composition of the present invention as a structural member of a MEMS device is used as a partition wall or as a part of a mechanical driving component . Examples of such MEMS devices include components such as a SAW (surface acoustic wave) filter, a BAW (bulk acoustic wave) filter, a gyro sensor, a display micro shutter, an image sensor, an electronic paper, an inkjet head, a biochip, . More specific examples are exemplified in Japanese Patent Publication Nos. 2007-522531, 2008-250200, and 2009-263544.

Since the photosensitive resin composition of the present invention is excellent in flatness and transparency, for example, the bank layer 16 and the planarization film 57 shown in Fig. 2 of Japanese Patent Laid-Open Publication No. 2011-107476, Japanese Patent Application Laid- The bank layer 221 and the third interlayer insulating film 216b shown in Fig. 10 of Japanese Patent Application Laid-Open No. 2010-27591, the barrier layer 12 and the planarization film 102 described in Fig. 4 (a) The second interlayer insulating film 125 and the third interlayer insulating film 126 described in FIG. 4A of JP 2009-128577 A, the planarization film 12 described in FIG. 3 of JP 2010-182638 A, The insulating film 14 and the like.

(Touch panel display device)

A touch panel display device of the present invention comprises a capacitive input device having a cured product of the present invention. Further, the capacitance type input device of the present invention is characterized by having the film of the present invention.

It is preferable that the capacitive input device of the present invention has at least the following elements (1) to (5) on the noncontact side of the front plate and the above-mentioned (4) is the heat treatment of the present invention.

(1) Mask layer

(2) a plurality of first transparent electrode patterns formed by extending a plurality of pad portions in a first direction through connection portions

(3) a plurality of second transparent electrode patterns, which are electrically insulated from the first transparent electrode pattern and are formed of a plurality of pad portions extending in a direction crossing the first direction,

(4) An insulating layer for electrically insulating the first transparent electrode pattern and the second transparent electrode pattern

(5) A method of manufacturing a semiconductor device, which is electrically connected to at least one of the first transparent electrode pattern and the second transparent electrode pattern, and which is different from the first transparent electrode pattern and the second transparent electrode pattern

The capacitive input device of the present invention preferably further includes a transparent protective layer so as to cover all or a part of the elements (1) to (5), and it is preferable that the transparent protective layer is a cured film of the present invention desirable.

First, the configuration of the capacitive input device will be described. 3 is a cross-sectional view showing the configuration of the capacitance type input device. 3, the capacitive input device 30 includes a front plate 31, a mask layer 32, a first transparent electrode pattern 33, a second transparent electrode pattern 34, an insulating layer 35, a conductive element 36, and a transparent protective layer 37. [

The front plate 31 is formed of a light-transmitting substrate such as a glass substrate, and tempered glass typified by Gorilla glass of Corning Inc. can be used. 3, the side on which the respective elements of the front surface plate 31 are provided is called a non-contact surface. In the capacitive input device 30 of the present invention, a finger or the like is brought into contact with the contact surface (the surface opposite to the non-contact surface) of the front plate 31, and the like. Hereinafter, the front plate may be referred to as a &quot; substrate &quot;.

On the non-contact surface of the front plate 31, a mask layer 32 is provided. The mask layer 32 is a frame-like pattern around the display area formed on the noncontact side of the front panel of the touch panel, and is formed so that the surrounding wiring and the like are not seen.

As shown in Fig. 4, the capacitive input device of the present invention is provided with a mask layer 32 so as to cover a part of the area of the front plate 31 (an area other than the input surface in Fig. 4). As shown in Fig. 4, the front plate 31 may have an opening 38 formed in a part thereof. The opening portion 38 can be provided with a mechanical switch by pressing.

5, a plurality of first transparent electrode patterns 33 formed by extending a plurality of pad portions in a first direction on a contact surface of the front plate 31, and a plurality of first transparent electrode patterns 33 A plurality of second transparent electrode patterns 34 electrically insulated from the first transparent electrode patterns 33 and formed of a plurality of pad portions extending in a direction crossing the first direction, An insulating layer 35 for electrically insulating the insulating layer 34 is formed. The first transparent electrode pattern 33, the second transparent electrode pattern 34 and the conductive element 36 to be described later are formed of a transparent conductive material such as ITO (Indium Tin Oxide) or IZO (Indium Zinc Oxide) A conductive metal oxide film can be formed. As such a metal film, an ITO film; Metal films of Al, Zn, Cu, Fe, Ni, Cr, and Mo; And a metal oxide film such as SiO ₂ . At this time, the film thickness of each element can be set to 10 to 200 nm. Further, the electrical resistance may be reduced in order to make the amorphous ITO film into a polycrystalline ITO film by firing. The first transparent electrode pattern 33, the second transparent electrode pattern 34 and the conductive element 36 to be described later can be manufactured using a photosensitive transfer material having a photosensitive resin composition using the conductive fibers have. In addition, when a first conductive pattern or the like is formed by ITO or the like, paragraphs 0014 to 0016 of Japanese Patent No. 4506785 can be referred to.

At least one of the first transparent electrode pattern 33 and the second transparent electrode pattern 34 is formed on both the noncontact surface of the front plate 31 and the surface opposite to the front plate 31 of the mask layer 32 Area. &Lt; / RTI &gt; 3, the second transparent electrode pattern is provided over both the noncontact surface of the front surface plate 31 and the surface opposite to the front surface plate 31 of the mask layer 32. As shown in Fig.

The first transparent electrode pattern 33 and the second transparent electrode pattern 34 will be described with reference to FIG. 5 is an explanatory view showing an example of a first transparent electrode pattern and a second transparent electrode pattern according to the present invention. As shown in Fig. 5, the first transparent electrode pattern 33 is formed by extending the pad portion 33a in the first direction through the connection portion 33b. The second transparent electrode pattern 34 is electrically insulated by the first transparent electrode pattern 33 and the insulating layer 35 and is arranged in a direction crossing the first direction As shown in Fig. Here, when the first transparent electrode pattern 33 is formed, the pad portion 33a and the connection portion 33b may be integrally formed. Alternatively, only the connection portion 33b may be formed, The second transparent electrode pattern 34 may be formed (patterned) as a single body. When the pad portion 33a and the second transparent electrode pattern 34 are integrally formed (patterned), a part of the connection portion 33b and a part of the pad portion 33a are connected as shown in Fig. 5, Each layer is formed by the insulating layer 35 so that the first transparent electrode pattern 33 and the second transparent electrode pattern 34 are electrically insulated from each other.

In Fig. 3, a conductive element 36 is provided on the side of the mask layer 32 opposite to the front face plate 31. The conductive element 36 is electrically connected to at least one of the first transparent electrode pattern 33 and the second transparent electrode pattern 34 and the first transparent electrode pattern 33 and the second transparent electrode pattern 34, Is a different element. In Fig. 3, a diagram is shown in which the conductive element 36 is connected to the second transparent electrode pattern 34. Fig.

In Fig. 3, a transparent protective layer 37 is provided so as to cover all the components. The transparent protective layer 37 may be configured to cover only a part of each constituent element. The insulating layer 35 and the transparent protective layer 37 may be made of the same material or different materials.

&Lt; Capacitive input device, and touch panel display device provided with capacitive input device >

The capacitive input device obtained by the manufacturing method of the present invention and the touch panel display device provided with the capacitive input device as a component are described in " Latest Touch Panel Technology " (issued on July 6, 2009, (2004, 12), FPD International 2009 Forum T-11 Lecture Textbook, Cypress Semiconductor Corporation Application Note AN2292 can be applied to the design of "Touch Panel Technology and Development", CMC Publishing have.

&Lt; Touch panel and manufacturing method thereof &

The touch panel of the present invention is a touch panel in which all or a part of the insulating layer is formed by heat treatment of the resin composition of the present invention. The touch panel of the present invention preferably has at least a transparent substrate, an ITO electrode, and an insulating layer.

The touch panel display device of the present invention is preferably a touch panel display device having the touch panel of the present invention.

The method of manufacturing a touch panel of the present invention is a method of manufacturing a touch panel having a transparent substrate, an ITO electrode, and an insulating layer, wherein the photosensitive resin composition for inkjet application of the present invention is applied by an inkjet coating method A step of applying a mask having an opening pattern of a predetermined shape on the resin composition and irradiating with an active energy ray to expose the resin composition, a step of developing the resin composition after exposure, and a step of heating the resin composition after development to produce an insulating layer Process.

As the transparent substrate in the touch panel of the present invention, a glass substrate, a quartz substrate, a transparent resin substrate and the like are preferably used.

The inkjet coating in the step of applying the photosensitive resin composition for inkjet coating of the present invention to the ITO electrode by the inkjet coating method can be performed in the same manner as in the above-described coating step, and the preferable embodiment is also the same. In the above step, at least a part of the applied photosensitive resin composition of the present invention may be in contact with the ITO electrode.

The step of carrying out exposure by carrying a mask having an opening pattern of a predetermined shape on the resin composition and performing the activation energy ray irradiation and the step of developing the resin composition after exposure can be carried out in the same manner as in the above exposure step, to be.

The step of heating the resin composition after the development to produce the insulating layer can be carried out in the same manner as the above-mentioned heat treatment step, and the preferable embodiment is also the same.

As an example of the ITO electrode pattern in the touch panel of the present invention, the above-described pattern shown in Fig. 5 is preferably used.

Example

Hereinafter, the present invention will be described in more detail by way of examples. The materials, the amounts used, the ratios, the contents of processing, the processing procedures, and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention is not limited to the following specific examples. Unless specifically stated, &quot; part &quot; and &quot;% &quot; are based on mass.

In the following examples, the following symbols respectively represent the following compounds.

MATHF: 2-Tetrahydrofuranyl methacrylate (Synthesis)

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

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

NBMA: n-butoxymethyl acrylamide [manufactured by Mitsubishi Rayon Co., Ltd.]

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

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

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

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

DCPM: dicyclopentanyl methacrylate (manufactured by Hitachi Kasei Kogyo Co., Ltd.)

BzMA: Benzyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)

V-601: Dimethyl 2,2'-azobis (2-methylpropionate) (manufactured by Wako Pure Chemical Industries, Ltd.)

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

PGMEA: Propylene glycol monomethyl ether acetate

MEDG: diethylene glycol ethyl methyl ether (manufactured by Tohoku Kagaku Kogyo Co., Ltd., high solvation EDM)

<Synthesis of MATHF>

Methacrylic acid (86 g, 1 mol) was cooled to 15 占 폚 and camphorsulfonic acid (4.6 g, 0.02 mol) was added. 2-dihydrofuran (71 g, 1 mol, 1.0 equivalent) was added dropwise to the solution. 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 was filtered off and concentrated under reduced pressure at 40 ° C or lower. 125 g of tetrahydrofuran-2-yl methacrylate (MATHF) having a boiling point (bp.) Of 54 to 56 ° C / 3.5 mmHg as a distillate was obtained as a colorless oil (yield: 80%).

&Lt; Measurement method of acid value >

The acid value of the polymer was measured by titration using potassium hydroxide.

<Preparation of Dispersion D1>

A dispersion of the following composition was combined and mixed with 17,000 parts of zirconia beads (0.3 mm?) And dispersed for 12 hours using a paint shaker. The zirconia beads (0.3 mm?) Were filtered to obtain a dispersion D1.

· Titanium dioxide [trade name: TTO-51 (C), average primary particle diameter: 10 to 30 nm, manufactured by Ishihara Sangyo Co., Ltd.): 1,875 parts

Compound 1 (Compound shown below, Mw = 13,800, 30% PGMEA solution): 2,200 parts

Solvent PGMEA (propylene glycol monomethyl ether acetate): 3,425 parts

In the compound 1, the sulfur atom bonded to the polymer chain may be bonded to the monomer unit of P1 or may be bonded to the monomer unit of P2.

The polymer chain is a random copolymerization skeleton composed of two kinds of monomer units represented by parentheses having P1 and P2 as subscripts.

<Preparation of Dispersions D2 to D17>

Dispersions D2 to D17 were obtained in the same manner as the preparation of Dispersion D1, except that TTO-51 (C) and Compound 1 were changed to those shown in Table 1, respectively.

In addition, abbreviations other than the above-mentioned abbreviations used in the dispersions shown in Table 1 are as follows. The values of "m" and "n" described in the compounds 1 to 5 are the average number of substitution, the values of "P1: P2" are the copolymerization ratios (mass ratio) Respectively. Further, "m ₁ ", "m ₂ ", "l ₁ ", and "l ₂ " described in the compound 6 represent the average substitution number.

Further, the compounds 1 to 6 and the compounds 7 to 13 described later were all synthesized with reference to the method described in Japanese Patent Application Laid-Open No. 2007-277514.

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

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

DISPERBYK-111: Dispersant other than Component S, manufactured by Big Chem Japan Co., Ltd.

DISPERBYK-2001: Dispersant other than Component S, manufactured by Big Chem Japan Co., Ltd.

Sol Spurs 41000: Dispersant other than component S, manufactured by Lubrizol

Compound 2: The following compound, Mw = 8,200, 30% PGMEA solution

Compound 3: The following compound, Mw = 4,800, 30% PGMEA solution

Compound 4: The following compound, Mw = 8,000, 30% PGMEA solution

Compound 5: The following compound, Mw = 3,200, 30% PGMEA solution

Compound 6: Mw = 3,300, 30% PGMEA solution, P1: P2 = 9.5: 0.5

In the compound 6, the sulfur atom bonded to the polymer chain (poly) may be bonded to the monomer unit of P1 or may be bonded to the monomer unit of P2.

The polymer chain is a random copolymer composed of two kinds of monomer units represented by parentheses having P1 and P2 as subscripts.

&Lt; Synthesis of Polymer P1 &

2-yl methacrylate tetrahydrofuran-2-yl (0.40 molar equivalent),

Methacrylic acid (0.10 molar equivalent),

100 parts of a total of methacrylic acid (3-ethyloxetan-3-yl) methyl (0.50 molar equivalent)

And a mixed solution of propylene glycol monomethyl ether acetate (PGMEA) (120 parts) was heated to 70 占 폚 under a nitrogen stream. While this mixed solution was stirred, a radical polymerization initiator V-601 (dimethyl-2,2'-azobis (2-methylpropionate)), Wako Pure Chemical Industries, Ltd., 12.0 parts) and PGMEA (80 parts) Was added dropwise over 3.5 hours. After completion of the dropwise addition, the PGMEA solution of the polymer P1 was obtained by reacting at 70 DEG C for 2 hours. PGMEA was further added to adjust the solid content concentration to 40 mass%.

The polymer P1 thus obtained had a weight average molecular weight (Mw) of 15,000 as measured by gel permeation chromatography (GPC). The acid value was 45 mg KOH / g.

&Lt; Synthesis of Polymers P2 to P10 >

Except that the respective monomers used in the synthesis of the polymer P1 were changed to the monomers forming the constituent units described in Table 2 and the amounts of the monomers forming the respective constituent units were changed to those described in Table 2, Polymers P2 to P10 were synthesized, respectively. The amount of the radical polymerization initiator V-601 was adjusted so that the respective polymers had the molecular weights shown in Table 2, respectively.

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

(Example 1)

&Lt; Preparation of Photosensitive Resin Composition >

And the mixture was mixed to obtain a homogeneous solution. The solution was filtered through a polyethylene filter having a pore size of 0.2 μm to prepare a photosensitive resin composition of Example 1. Various evaluations to be described later were conducted using the obtained photosensitive resin composition. The evaluation results are shown in Table 3 below.

Propylene glycol monomethyl ether acetate: 191.1 parts

A 0.2% PGMEA solution of the following compound I-1 (CMTU, manufactured by Toyo Kasei Kogyo Co., Ltd.): 25.7 parts

30% PGMEA solution of polymer P1: 263.3 parts

Photoacid generator B-1 (compound shown below): 5.1 parts

· Epoxy resin, manufactured by Mitsubishi Kagaku Co., Ltd., epoxy equivalent: 200 to 220 g / eq]: 17.9 parts

· 3-glycidoxypropyltrimethoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.): 4.5 parts

· Igarox 1726 (antioxidant, made by BASF): 3.0 parts

2.0% of a nonionic surfactant containing perfluoroalkyl group [F-554, manufactured by DIC Corporation] PGMEA solution: 11.0 parts

Dispersion D1: 478.4 parts

<Synthesis of B-1>

According to the following method, the above-mentioned B-1 was synthesized.

Aluminum chloride (10.6 g) and 2-chloropropionyl chloride (10.1 g) were added to a stirring solution of 2-naphthol (10 g) and chlorobenzene (30 ml), and the mixture was heated to 40 ° C and reacted for 2 hours. Under ice cooling, 4N HCl aqueous solution (60 mL) was added dropwise to the reaction solution, 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 DEG C for 1 hour. 2N HCl aqueous solution (60 mL) was added thereto to separate the liquid. The organic layer was concentrated, and the crystals were reslurried with diisopropyl ether (10 mL) And dried to obtain a ketone compound (6.5 g).

Acetic acid (7.3 g) and a 50 mass% hydroxylamine aqueous solution (8.0 g) were added to the resulting solution of the ketone compound (3.0 g) and methanol (30 ml), and the mixture was heated to reflux. After allowing to stand and cool, water (50 mL) was added, and the precipitated crystals were filtered, washed with cold methanol, and dried to obtain an oxime compound (2.4 g).

The obtained oxime compound (1.8 g) was dissolved in acetone (20 mL), triethylamine (1.5 g) and p-toluenesulfonyl chloride (2.4 g) were added under ice-cooling. The temperature was raised to room temperature Lt; / RTI &gt; Water (50 mL) was added to the reaction solution, and the precipitated crystals were filtered out, and then slurry was rinsed with methanol (20 mL), followed by filtration and drying to obtain 2.3 g of B-1.

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

&Lt; Evaluation of residual film ratio of unexposed portion &

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

Subsequently, development was carried out by a submerged filling method at 23 DEG C for 15 seconds with a 0.5 mass% aqueous KOH solution, and further rinsed with ultrapure water for 10 seconds. Thereafter, by measuring the film thickness further, the residual film ratio after development for the case where the original film thickness (1.0 탆) was 100% was obtained. The evaluation criteria are as follows. 1 or 2 is a practical range.

1: The residual film ratio after development is 90% or more.

2: The residual film ratio after development is 80% or more and less than 90%.

3: The residual film ratio after development is less than 80%.

&Lt; Evaluation of resolution >

The obtained photosensitive resin composition was applied on a 100 mm x 100 mm glass substrate (trade name: XG, manufactured by Corning) treated with hexamethyldisilazane (HMDS) for 3 minutes by a spin coater so as to have a film thickness of 2.0 m, (Prebaked) on a hot plate at 90 DEG C for 120 seconds.

Subsequently, the resist film was exposed through a mask having a 1% to 60% line-and-space 1: 1 gradation at an energy intensity of 20 mW / cm 2 and 200 mJ / cm 2 using a ghi line high pressure mercury lamp exposing machine.

Subsequently, development was carried out with a 0.5% KOH aqueous solution at 23 DEG C for 15 seconds by dip filling, and further rinsed with ultra pure water for 10 seconds. Subsequently, a pattern was obtained by heating at 220 DEG C for 45 minutes. This pattern was observed with an optical microscope.

This operation was started from the width of the line and space of the mask of 50 .mu.m to 5 .mu.m from the width of 10 .mu.m and narrower by 1 .mu.m from the width of 10 .mu.m to the minimum width of the pattern of optimum exposure. 1 or 2 is a practical range.

1: Resolution was 5 탆 or less.

2: The resolution was more than 5 탆 and not more than 10 탆.

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

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

&Lt; Evaluation of transmittance &

The photosensitive resin composition thus obtained was coated on a glass substrate (trade name: XG, manufactured by Corning) having a size of 100 mm x 100 mm by a spin coater so as to have a thickness of 1.0 탆 and dried (prebaked) on a hot plate at 90 캜 for 120 seconds. The coating film was subjected to heat treatment (post baking) in an oven at 220 占 폚 for 245 minutes, and post-baking spectroscopy was measured with MCPD-3000 manufactured by Otsuka Denshi Co., Ltd. The transmittance of 400 nm was measured according to the following evaluation criteria I appreciated. 1 or 2 is a practical range.

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

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

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

&Lt; Evaluation of visibility of ITO &

A pattern of ITO was previously formed on a glass substrate (trade name: XG, manufactured by Corning) having a size of 100 mm x 100 mm, and the obtained photosensitive resin composition was coated with a spin coater so as to have a film thickness of 1.0 탆. Dried (prebaked).

Subsequently, the entire surface of the substrate was exposed to light with an energy intensity of 20 mW / cm 2 and 200 mJ / cm 2 using a ghi line high-pressure mercury lamp exposer.

Subsequently, the dried film of the photosensitive resin composition was placed on the ITO pattern by heating at 220 DEG C for 45 minutes. The obtained substrate was visually observed while forming a tilt in the bright room, and visibility was evaluated in comparison with the case where the photosensitive resin composition was not provided on the ITO pattern. Also, the better the evaluation criteria are, the less ITO pattern is visible. 1 or 2 is a practical range.

1: ITO patterns are hardly visible.

2: The patterns of ITO are slightly visible.

3: The pattern of ITO clearly appears.

&Lt; Evaluation of haze (transparency) >

The obtained photosensitive resin composition was coated on a glass substrate (trade name: XG, Corning) having a size of 100 mm x 100 mm with a spin coater so as to have a dry film thickness of 2.0 탆 and dried (prebaked) on a hot plate at 80 캜 for 120 seconds. . The coated film was subjected to heat treatment (post baking) in an oven at 120 캜 for 15 minutes, and the post-baking haze was measured with a plastic product test method (JIS K7136 &amp;num; (Haze value) was measured according to JIS K7361, ASTM D1003).

The haze value refers to a value expressed by a ratio (%) of diffuse transmission light to all-light transmission light. The smaller the haze value, the higher the transparency.

<Evaluation of Refractive Index>

The obtained photosensitive resin composition was coated on a silicon wafer substrate using a spinner and dried at 80 DEG C for 120 seconds to form a film having a thickness of 0.5 mu m. This substrate was exposed using an ultra-high pressure mercury lamp at 200 mJ / cm 2 (measured by i-line), and then heated in an oven at 220 ° C for 45 minutes.

The refractive index of the cured film at 589 nm was measured using an ellipsometer VUV-VASE (manufactured by J. A. Ullam Japan Co., Ltd.). It is preferable that the refractive index is high, and it is more preferable to be 1.70 or more.

(Examples 2 to 35 and Comparative Examples 1 to 5)

In Examples 2 to 35 and Comparative Examples 1 to 5, a photosensitive resin composition was prepared in the same manner as in Example 1 except that the dispersion and the component A (polymer) were changed to those shown in Table 3, respectively, and each evaluation was carried out.

In Examples 20 to 24, components other than the dispersion and component A were further changed as shown below, and a photosensitive resin composition was prepared.

Example 20: The photoacid generator B-1 was changed to the following CGI-1397 (manufactured by BASF).

Example 21: The photo acid generator B-15.1 was changed to the following B-22.55 parts and 9,10-dibutoxyanthracene DBA (Kawasaki Kasei Kogyo KK) to 2.55 parts.

Example 22: JER157S65 was changed to the following EHPE-3150 (manufactured by Daicel Chemical Industries, Ltd.).

Example 23: JER157S65 was changed to EPICLON HP-7200HH (epoxy resin, manufactured by DIC Corporation).

Example 24: Igarox 1726 was changed to TINUVIN 405 (manufactured by BASF).

<Synthesis of B-2>

Α- (p-toluenesulfonyloxyimino) phenylacetonitrile (B-2) was synthesized according to the method described in paragraph 0108 of Japanese Patent Publication No. 2002-528451.

As is clear from the results shown in Table 3, the photosensitive resin composition of the present invention had a low haze and maintained a high transmittance even after heating. On the other hand, in the photosensitive resin composition of the comparative example, it was found that the transmittance after heating was low and the haze was lowered.

<Preparation of Dispersions D18 to D45>

Dispersions D18 to D45 were obtained in the same manner as in the preparation of Dispersion D1, except that TTO-51 (C) and Compound 1 were changed to those shown in Table 4, respectively.

Compounds 7 to 13 described in Table 4 are shown below.

Compound 7: Mw = 4,000, 30% PGMEA solution, P1: P2 = 86.5 mass%: 13.5 mass%

Compound 8: The following compound, Mw = 4,700, 30% PGMEA solution

Compound 9: The following compound, Mw = 4,800, 30% PGMEA solution

Compound 10: The following compound, Mw = 4,400, 30% PGMEA solution

Compound 11: The following compound, Mw = 6,300, 30% PGMEA solution

Compound 12: The following compound, Mw = 4,300, 30% PGMEA solution

Compound 13: The following compound, Mw = 6,200, 30% PGMEA solution

&Lt; Synthesis of polymers P11 to P15 >

MEDG (89 g) was placed in a three-necked flask, and the temperature was raised to 90 占 폚 in a nitrogen atmosphere. (Equivalent to 10 mol% of the total monomer components), MATHF (40 mol% of the total monomer components), GMA (corresponding to 35 mol% of the total monomer components), HEMA 15 mol%) and V-65 (corresponding to 3 mol% based on the total amount of 100 mol% of the monomer components) were dissolved and added dropwise over 2 hours. After completion of dropwise addition, the mixture was stirred for 2 hours to complete the reaction. Polymer P11 was thereby obtained. Also, the ratio of the total amount of MEDG to the other ingredients was 70:30. That is, a polymer solution having a solid content concentration of 30% was prepared.

Polymers P12 to P15 were synthesized in the same manner as in the synthesis of the polymer P11 except that the type of the monomer to be used and the polymerization initiator were changed as shown in the following table.

In Table 5, numerical values not specifically showing units are in mol%. The numerical value of the polymerization initiator is mol% when the monomer component is taken as 100 mol%.

The solid content concentration can be calculated by the following equation.

Solid concentration: monomer weight / (monomer weight + solvent weight) x 100 (unit: mass%)

Further, when V-601 was used as the initiator, the reaction temperature was set to 90 ° C, and when V-65 was used, the reaction temperature was set to 70 ° C.

(Example 36)

&Lt; Preparation of Photosensitive Resin Composition >

The solution was mixed with the following composition to prepare a homogeneous solution, which was then filtered using a polyethylene filter having a pore size of 0.2 mu m to prepare a photosensitive resin composition of Example 36. [ Various evaluations to be described later were conducted using the obtained photosensitive resin composition. The evaluation results are shown in Tables 9 to 11 below.

Solvent (PGMEA): 307.5 parts

Compound I-1: 0.02 part

Polymer P11: 100.0 parts

Photoacid generator B-1: 1.9 parts

· JER157S65: 6.9 parts

KBM-403: 1.7 parts

F-554: 0.08 part

Dispersion D18: 181.7 parts

&Lt; Examples 37 to 135 >

A photosensitive resin composition was prepared in the same manner as in Example 36 except that the polymer, photoacid generator, sensitizer and other components shown in Tables 6 to 8 were changed. The addition amounts of the respective component amounts in Tables 6 to 8 indicate mass% or mass parts.

Details of the abbreviations other than those described in Tables 6 to 8 are as follows.

&Lt;

B-3: GSID-26-1, triarylsulfonium salt (manufactured by BASF)

<Increase / decrease>

G-1: DBA [9,10-dibutoxyanthracene, manufactured by Kawasaki Kasei Kogyo Co., Ltd.]

&Lt; Basic compound >

I-2: 1,5-Diazabicyclo [4.3.0] -5-nonene (manufactured by Tokyo Kasei Kogyo Co., Ltd.)

(Example 136)

In the active matrix type liquid crystal display device shown in Fig. 1 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 136. [ That is, after the photosensitive resin composition of Example 5 was spin-coated on the substrate and prebaked (90 DEG C / 120 seconds) on a hot plate, i-line (365 nm) was irradiated with 45 mJ / Intensity of 20 mW / cm 2), and then developed with an aqueous alkali solution to form a pattern, followed by heat treatment at 230 ° C for 30 minutes to form a cured film 17 as an interlayer insulating film.

As a result of applying a driving voltage to the obtained liquid crystal display device, it was found that the liquid crystal display device exhibited good display characteristics and was highly reliable.

(Example 137)

An organic EL display device using a thin film transistor (TFT) was produced by the following method (see Fig. 2).

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. Subsequently, 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 in the TFT 1 or in a subsequent step to the TFT 1. [

In order to planarize the irregularities formed by the formation of the wirings 2, the flattening film 4 was formed on the insulating film 3 in a state of embedding the irregularities by the wirings 2. The planarizing film 4 was formed on the insulating film 3 by spin-coating the photosensitive resin composition of Example 5 on the substrate and prebaking (90 DEG C / 120 seconds) on a hot plate, , An i-line (365 nm) was irradiated with 45 mJ / cm 2 (energy intensity 20 mW / cm 2) and then developed with an alkali aqueous solution to form a pattern and subjected to heat treatment at 230 ° C for 30 minutes.

The coating properties upon application of the photosensitive resin composition were satisfactory, and wrinkles and cracks were not observed in the cured films obtained after exposure, development and firing. In addition, the average step of the wiring 2 was 500 nm, and the film thickness of the prepared planarization film 4 was 2,000 nm.

Subsequently, a bottom-emission organic EL device was formed on the obtained planarization film 4. Then, First, a first electrode 5 made of ITO was formed on the flattening film 4 by connecting it to the wiring 2 through 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 an ITO etchant. Thereafter, the resist pattern was peeled off at 50 占 폚 using a resist stripping solution (Remover 100, manufactured by AZ Electronic Materials Co., Ltd.). The thus obtained first electrode 5 corresponds to the anode of the organic EL element.

Then, an insulating film 8 having a shape covering the periphery of the first electrode 5 was formed. The insulating film 8 was formed in the same manner as above using the photosensitive resin composition of Example 5. By providing the insulating film 8, a short circuit can be prevented 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 through a desired pattern mask in a vacuum evaporation apparatus. Then, a second electrode made of Al was formed on the entire upper surface of the substrate. The obtained substrate was taken out 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 were connected to each organic EL element was obtained. As a result of applying a voltage through the driving circuit, it was found that the organic EL display device exhibited good display characteristics and was highly reliable.

(Example 138)

A touch panel display device was produced by using the curable resin material of the present invention having high refractive index by the method described below.

&Lt; Formation of first transparent electrode pattern >

[Formation of transparent electrode layer]

A front plate of a tempered glass (300 mm x 400 mm x 0.7 mm) having a mask layer formed therein was introduced into a vacuum chamber and an ITO target (indium: tin = 95: 5 (molar ratio)) having a SnO ₂ content of 10% , A 40 nm thick ITO thin film was formed by DC magnetron sputtering (conditions: substrate temperature: 250 캜, argon pressure: 0.13 Pa, oxygen pressure: 0.01 Pa) to obtain a front plate having a transparent electrode layer. The surface resistance of the ITO thin film was 80? / ?.

Then, a commercially available etching resist was coated on ITO and dried to form an etching resist layer. The pattern exposure was performed at an exposure amount of 50 mJ / cm 2 (i line) with a distance between the surface of the exposure mask (a quartz exposure mask having a transparent electrode pattern) and the etching resist layer set at 100 m, Lt; 0 &gt; C for 30 minutes to obtain a front plate having a transparent electrode layer and a photocurable resin layer pattern for etching formed thereon.

The front plate on which the transparent electrode layer and the photocurable resin layer pattern for etching were formed was immersed in an etching bath containing ITO etchant (hydrochloric acid, potassium chloride aqueous solution, liquid temperature of 30 DEG C) for 100 seconds to remove the exposed region Of the transparent electrode layer was dissolved and removed to obtain a front panel having a transparent electrode layer pattern with an etching resist layer pattern.

Next, a front plate having a mask layer and a first transparent electrode pattern formed by removing the photo-curable resin layer for etching was immersed in a resist stripper for exclusive use having a transparent electrode layer pattern with an etching resist layer pattern attached thereto, .

[Formation of insulating layer]

The photosensitive resin composition of Example 36 was applied and dried (film thickness: 1 占 퐉, 90 占 폚 for 120 seconds) on the front plate on which the mask layer and the first transparent electrode pattern were formed to obtain a photosensitive resin composition layer. The pattern exposure was performed at an exposure amount of 50 mJ / cm 2 (i line) by setting the distance between the exposure mask (quartz exposure mask having an insulating layer pattern) surface and the photosensitive resin composition layer at 30 μm.

Subsequently, development was carried out with a 2.38 mass% aqueous solution of tetramethylammonium hydroxide at 23 占 폚 for 15 seconds by dip filling, and further rinsed with ultrapure water for 10 seconds. Subsequently, post baking treatment was performed at 220 캜 for 45 minutes to obtain a front plate having a mask layer, a first transparent electrode pattern, and an insulating layer pattern formed thereon.

&Lt; Formation of second transparent electrode pattern >

[Formation of transparent electrode layer]

The front plate formed up to the insulating layer pattern in the same manner as the formation of the first transparent electrode pattern was subjected to DC magnetron sputtering (conditions: substrate temperature: 50 캜, argon pressure: 0.13 Pa, oxygen pressure: 0.01 Pa) ITO thin film was formed and a front panel having a transparent electrode layer was obtained. The surface resistance of the ITO thin film was 110? / ?.

A first transparent electrode pattern, an insulating layer pattern formed by using the photosensitive resin composition of Example 36, a transparent electrode layer, a front surface plate on which an etching resist pattern was formed, and the like were formed using a commercially available etching resist in the same manner as the formation of the first transparent electrode pattern. (Post baking treatment; at 130 占 폚 for 30 minutes).

The mask layer, the first transparent electrode pattern, the insulating layer pattern formed by using the curable resin composition of Example 36, and the second transparent electrode pattern were removed by etching in the same manner as the formation of the first transparent electrode pattern, A front plate on which a pattern was formed was obtained.

&Lt; Formation of a conductive element different from the first and second transparent electrode patterns &

The front plate on which the first transparent electrode pattern, the insulating layer pattern formed by using the photosensitive resin composition of Example 36, and the second transparent electrode pattern were formed in the same manner as in the formation of the first and second transparent electrode patterns was formed as a DC magnetron And a front plate having an aluminum (Al) thin film having a thickness of 200 nm was obtained by sputtering.

A first transparent electrode pattern was formed by using a commercially available etching resist, an insulating layer pattern formed by using the photosensitive resin composition of Example 36, a second transparent electrode pattern, and a second transparent electrode pattern were formed in the same manner as the formation of the first and second transparent electrode patterns, A front face plate on which an etching resist pattern was formed was obtained (post baking treatment: 130 DEG C for 30 minutes).

The mask layer, the first transparent electrode pattern, and the photosensitive resin composition of Example 36 were removed by etching (30 占 폚 for 50 seconds) and removing the etching resist layer (45 占 폚 for 200 seconds) A second transparent electrode pattern, and a front plate on which conductive elements different from those of the first and second transparent electrode patterns were formed were obtained.

&Lt; Formation of transparent protective layer &

The photosensitive resin composition of Example 36 was coated and dried (film thickness 1 占 퐉, 90 占 폚 for 120 seconds) on the front plate having the conductive elements other than the first and second transparent electrode patterns formed in the same manner as the formation of the insulating layer Thereby obtaining a photosensitive resin composition film. The mask layer, the first transparent electrode pattern, and the photosensitive layer of Example 36 were subjected to front surface exposure at an exposure dose of 50 mJ / cm 2 (i line) without passing through an exposure mask, and development, post exposure (1,000 mJ / cm 2) The insulating layer pattern formed using the resin composition, the second transparent electrode pattern, and the insulating layer formed by using the photosensitive resin composition of Example 36 (the entirety of the conductive elements different from the first and second transparent electrode patterns Transparent protective layer) was laminated on the front plate.

&Lt; Fabrication of Image Display Device (Touch Panel)

An image display device having a capacitive input device as a constituent element was manufactured by bonding a previously prepared front panel to a liquid crystal display element manufactured by the method described in JP-A-2009-47936.

<Evaluation of Front Panel and Image Display Device>

There is no problem in the conductivity of each of the first transparent electrode pattern, the second transparent electrode pattern, and the conductive elements different therefrom. On the other hand, the first transparent electrode pattern has insulation between the first transparent electrode pattern and the second transparent electrode pattern, Good display characteristics were obtained. In addition, the first and second transparent electrode patterns were hardly visually observed, and an image display apparatus having excellent display characteristics was obtained.

1: TFT (thin film transistor) 2: wiring
3: insulating film 4: planarization film
5: first electrode 6: glass substrate
7: Contact hole 8: Insulating film
10: liquid crystal display device 12: backlight unit
14, 15: glass substrate 16: TFT
17: curing film 18: contact hole
19: ITO transparent electrode 20: liquid crystal
22: Color filter 30: Capacitive input device
31: front plate 32: mask layer
33: first transparent electrode pattern 33a: pad portion
33b: connecting portion 34: second transparent electrode pattern
35: insulating layer 36: conductive element
37: transparent protective layer 38: opening

Claims (15)

(Component A) A polymer component comprising a polymer satisfying at least one of the following (1) and (2)
(1) a polymer having (a1) a structural unit having a group protected with an acid-decomposable group and (a2) a structural unit having a crosslinkable group,
(2) a polymer having (a1) a structural unit having a group protected with an acid-decomposable group, and (a2) a polymer having a structural unit having a crosslinkable group,
(Component S) A dispersing agent represented by the following formula (S) and having at least one acid group,
(Component B) Photoacid generators,
(Component C) metal oxide particles, and
(Component D) a solvent.

(In the formula (S), R ³ represents a linking group of (m + n), R ⁴ and R ⁵ each independently represent a single bond or a divalent linking group, A ² represents an organic pigment structure, , A group having a basic nitrogen atom, a urea group, a urethane group, a group having a radial oxygen atom, an alkoxysilyl group, a phenol group, an alkyl group, an aryl group, a group having an alkyleneoxy group, an imide group, an alkyloxycarbonyl group, A monovalent organic group containing at least one partial structure selected from the group consisting of an aminocarbonyl group, a carboxylate group, a sulfonamide group, an epoxy group, an isocyanate group and a hydroxyl group, n A ² and R ⁴ may be the same or different, m represents 0 to 8, n represents 2 to 9, m + n represents 3 to 10, P ² represents a polymer skeleton, and m P ² and R ⁵ may be the same or different) The method according to claim 1,
And the component C is a titanium oxide particle or a zirconium oxide particle. 3. The method according to claim 1 or 2,
Wherein A &lt; ^{2 &gt;} is a monovalent organic group containing at least one acid group. 4. The method according to any one of claims 1 to 3,
Wherein P ² is an acrylic resin skeleton. 5. The method according to any one of claims 1 to 4,
And the component A comprises a polymer satisfying the above-mentioned (1). 6. The method according to any one of claims 1 to 5,
(Component E) a crosslinking agent. 7. The method according to any one of claims 1 to 6,
(Component F) an antioxidant. Wherein at least the steps (a) to (c) are carried out in this order.
(a) a coating step of applying the photosensitive resin composition according to any one of claims 1 to 7 onto a substrate
(b) a solvent removing step of removing the solvent from the applied resin composition
(c) a heat treatment step of heat-treating the resin composition from which the solvent has been removed Comprising at least the steps (1) to (5) in this order.
(1) a coating step of applying the photosensitive resin composition according to any one of claims 1 to 7 onto a substrate
(2) a solvent removing step of removing the solvent from the applied resin composition
(3) an exposure step of exposing the resin composition from which the solvent has been removed to a pattern shape by an actinic ray
(4) a developing step of developing the exposed resin composition with an aqueous developing solution
(5) Heat treatment process for heat-treating the developed resin composition A cured product obtained by the process for producing a cured product according to claim 8 or the process for producing a resin pattern according to claim 9. A cured film formed by curing the photosensitive resin composition according to any one of claims 1 to 7. 12. The method of claim 11,
Wherein the cured film is an interlayer insulating film. A liquid crystal display device having the cured film according to claim 11 or 12. An organic EL display device having the cured film according to claim 11 or 12. A touch panel display device having the cured film according to claim 11 or 12.

Images