KR20130048696A - Positive-type photosensitive resin composition, method of producing cured film, cured film, liquid crystal display device, and organic electroluminescent display device - Google Patents

Abstract

PURPOSE: A positive type photosensitive resin composition is provided to have high sensitivity, to have high resistance to a stripping composition or NMP, to have excellent adhesion to a transparent electrode film or metal and etching resistance. CONSTITUTION: A positive type photosensitive resin composition contains a polymer component, photoacid generator, a solvent, and a silica compound which has two or more hydrolyzable silyl group and/or silanol group represented by chemical formula X1. The polymer component includes a polymer which has a structure unit having a group protected by an acid-decomposable group and a structure unit having a crosslinkable group; and/or a polymer which has a structure unit having a group protected by an acid-decomposable group and a crosslinkable group.

Description

POSITIVE-TYPE PHOTOSENSITIVE RESIN COMPOSITION, METHOD OF PRODUCING CURED FILM, CURED FILM, LIQUID CRYSTAL DISPLAY DEVICE, AND ORGANIC ELECTROLUMINESCENT DISPLAY DEV }

The present invention relates to a positive photosensitive resin composition, a method of forming a cured film, a cured film, a liquid crystal display device, and an organic EL display device. More specifically, it relates to a positive type photosensitive resin composition suitable for the formation of planarization films, protective films and interlayer insulating films of electronic components such as liquid crystal display devices, organic EL display devices, integrated circuit devices, solid-state imaging devices, and a method of forming a cured film using the same. will be.

In an electronic component such as a thin film transistor (hereinafter referred to as "TFT") type liquid crystal display element, a magnetic head element, an integrated circuit element, or a solid-state image sensor, an interlayer insulating film is generally formed to insulate between wirings arranged in layers. It is. As a material for forming the interlayer insulating film, a photosensitive resin composition is widely used in that it is preferable that the number of steps for obtaining the required pattern shape is small and the flatness is sufficient.

Among the electronic components, for example, in the TFT type liquid crystal display device, a transparent electrode film ITO is formed on the interlayer insulating film, and a wiring made of metal such as molybdenum (Mo) or titanium (Ti) is further formed thereon. Since it is manufactured through the process of forming a liquid crystal aligning film, an interlayer insulation film is exposed to high temperature conditions in the formation process of a transparent electrode film, or peeling liquid (mainly monoethanolamine (MEA)) of a resist used for pattern formation of an electrode, or liquid crystal aligning film formation. Because they will be exposed to the N-methylpyrrolidone (NMP) used in the city, sufficient resistance to them is necessary. Moreover, since an interlayer insulation film may be added to a dry etching process, sufficient resistance to dry etching is also required.

In addition, Japanese Unexamined Patent Publication No. 2009-258722 contains a specific acrylic acid structural unit that generates a carboxyl group by dissociating a dissociable group, which is alkali insoluble or alkali poorly soluble, and which becomes alkali-soluble when the acid dissociable group decomposes. , A resin containing a structural unit derived from an epoxy group-containing radically polymerizable monomer, a compound having two or more epoxy groups in a molecule (except the resin containing a structural unit composed of an epoxy group-containing radically polymerizable compound), wavelength Positive type photosensitive resin composition containing the compound which generate | occur | produces an acid by irradiation of actinic light of 300 nm or more is proposed.

Moreover, the positive photosensitive resin composition containing alkali-soluble resin (A), the photosensitive agent (B), and the specific silicon compound (C) is proposed by the international publication 2009/136647 pamphlet.

However, the photosensitive resin composition proposed in Japanese Patent Application Laid-Open No. 2009-258722 and International Publication No. 2009/136647 pamphlet is preferably a stripping solution of a resist (mainly monoethanolamine (MEA)) used after formation of an interlayer insulating film or a solvent. Since the resistance to NMP (N-methylpyrrolidone) is not high and the resistance to dry etching is not high, the display problem in a liquid crystal display device tends to occur, and improvement was calculated | required.

This invention is made | formed in view of the above circumstances, and solves the following subjects.

That is, the problem which this invention is trying to solve is the positive photosensitive resin composition which can obtain the cured film which is high in resist stripping solution and NMP, and excellent in dry etching resistance, and a display problem hardly arises also in a display apparatus, The said It provides the cured film obtained by hardening | curing the photosensitive resin composition, its formation method, and the organic electroluminescence display provided with the said cured film, and a liquid crystal display device.

In this situation, the inventors of the present invention have diligently studied and found that the above problems can be solved by using a silicon compound having a specific structure. This is because in the chemically amplified resist having a crosslinkable group, the alkoxysilyl compound functions effectively as a curing agent that binds to a crosslinkable group or a deprotected acid group. Specifically, the problem was solved by the following means <1> or <16>, more preferably by the following means <2> to <16>.

<1> (component A) The polymer component containing the polymer which satisfy | fills at least one of following (1) and (2),

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

(2) a polymer having a structural unit (a1) in which an acid group has a group protected by an acid-decomposable group, and (a2) a polymer having a structural unit having a crosslinkable group,

(Component C) a photoacid generator, and

(Component D) contains a solvent, and

(Component X) The positive photosensitive resin composition containing the silicon compound which has two or more hydrolyzable silyl groups and / or silanol groups represented by Formula (X1) in 1 molecule.

^Wherein at least one of R ^X1 to R ^X3 is a hydrolyzable group selected from the group consisting of an alkoxy group, a mercapto group, a halogen atom, an amide group, an acetoxy group, an amino group, an allyloxy group and an isopropenoxy group or Hydroxy group, and the remaining R ^X1 to R ^X3 each independently represent a hydrogen atom, a halogen atom or a monovalent organic substituent)

<2> The positive photosensitive resin composition according to <1>, wherein at least two of R ^X1 to R ^X3 in the structural unit (X1) are an alkoxy group.

<3> Positive photosensitive resin composition as described in <1> or <2> whose content of the said component X is 0.1 weight% or more with respect to the sum total of the component except the solvent of the resin composition.

<4> The positive photosensitive resin composition according to any one of <1> to <3>, wherein the structural unit (a1) is a structural unit having a residue in which a carboxyl group is protected by acetal or ketal.

<5> Positive photosensitive resin composition in any one of <1>-<4> whose said structural unit (a1) is a structural unit represented by Formula (a1-1).

(Wherein R ¹ and R ² each represent a hydrogen atom, an alkyl group or an aryl group, at least one of R ¹ and R ² is an alkyl group or an aryl group, R ³ represents an alkyl group or an aryl group, and R ¹ or R ² and R ³ may be linked 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)

<6> The positive photosensitive resin composition according to any one of <1> to <5>, wherein at least two of R ^X1 to R ^X3 of the structural unit (X1) are a methoxy group or an ethoxy group.

<7> Positive photosensitive resin composition in any one of <1>-<6> whose said structural unit (a2) is a structural unit which has at least 1 sort (s) chosen from an epoxy group and an oxetanyl group.

<8><1> to <7> according to any one of, the content W _A and the weight ratio of the amount W _B of component B in component _{A W A / W B = 98} /2 ~ 20/80 of a positive photosensitive Resin composition.

<9> Positive photosensitive resin composition in any one of <1>-<8> whose component C is an oxime sulfonate compound which has at least 1 of the oxime sulfonate residue represented by Formula (c0).

<10> (1) Process of apply | coating positive type photosensitive resin composition in any one of <1>-<9> on a board | substrate,

(2) removing the solvent from the applied photosensitive resin composition,

(3) Process of exposing photosensitive resin composition from which solvent was removed by actinic light,

(4) process of developing exposed photosensitive resin composition with aqueous developing solution, and

(5) The formation method of the cured film containing the post-baking process of thermosetting the developed photosensitive resin composition.

<11> The method for forming a cured film according to <10>, comprising a step of exposing the entire surface of the photosensitive resin composition developed after the developing step and before the post-baking step.

<12> The method for forming a cured film according to <10> or <11>, further comprising (6) performing a dry etching process on the substrate having a cured film obtained by thermosetting.

<13> Cured film formed by the formation method of the cured film in any one of <10>-<12>.

<14> The cured film as described in <13> which is an interlayer insulation film.

<15> The organic electroluminescence display or liquid crystal display device provided with the cured film as described in <13> or <14>.

<16> The chemical-resistance improving agent of the positive photosensitive resin composition characterized by containing the silicon compound which has 2 or more of hydrolysable silyl groups and / or silanol groups represented by Formula (X1) in 1 molecule.

^Wherein at least one of R ^X1 to R ^X3 is a hydrolyzable group selected from the group consisting of an alkoxy group, a mercapto group, a halogen atom, an amide group, an acetoxy group, an amino group, an allyloxy group and an isopropenoxy group or Hydroxy group, and the remaining R ^X1 to R ^X3 each independently represent a hydrogen atom, a halogen atom or a monovalent organic substituent)

(Effects of the Invention)

ADVANTAGE OF THE INVENTION According to this invention, the positive photosensitive resin composition which is high in resistance to MEA and NMP, and excellent in dry etching resistance, and which can hardly produce a display problem also in a display apparatus, hardening obtained by hardening the said photosensitive resin composition An organic EL display device and a liquid crystal display device provided with the film, the formation method, and the said cured film could be provided.

1 shows a configuration conceptual diagram of an example of an organic EL display device. Typical sectional drawing of the board | substrate in a bottom emission type organic electroluminescence display is shown, and it has the planarization film 4. As shown in FIG.
2 shows a configuration conceptual diagram of an example of a liquid crystal display device. Typical sectional drawing of the active-matrix board | substrate in a liquid crystal display device is shown, and it has the cured film 17 which is an interlayer insulation film.

Hereinafter, the present invention will be described in detail.

In addition, description of "lower limit-an upper limit" shows "lower limit or more and an upper limit or less" in the specification, and description of "upper limit-lower limit" represents "upper limit or less, lower limit or more". That is, the numerical range containing an upper limit and a lower limit is shown.

In addition, "(component C) photo-acid generator etc." is also called "component C" etc. simply, "The structural unit which has the residue in which the (a1) acidic group was protected by the acid-decomposable group", etc. "Structural unit (a1)" etc. Also called.

In addition, when both or any one of "acrylate" and "methacrylate" are referred to as "(meth) acrylate", when both or any of "acryl" and "methacryl" are referred to as "(meth) acryl" May be described respectively.

(Positive photosensitive resin composition)

The positive photosensitive resin composition (henceforth simply called "photosensitive resin composition") of this invention is a polymer component containing the polymer which satisfy | fills at least one of (component A) following (1) and (2),

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

(2) a copolymer having (a1) a polymer having a structural unit having a group protected by an acid-decomposable group, (a2) a polymer having a structural unit having a crosslinkable group, and (a2) a structural unit having a crosslinkable group, (component C) The silicon compound which has a photo-acid generator, the (component D) solvent, and the (component X) hydrolyzable silyl group and / or silanol group represented by Formula (X1) in 2 or more molecules in 1 molecule.

Moreover, it is preferable that the photosensitive resin composition of this invention contains the copolymer which does not have a structural unit which has an acidic radical protected group by the acid-decomposable group, and has a structural unit which has an acidic radical and a crosslinkable group at least.

The photosensitive resin composition of this invention contains specific resin (component A), a photo-acid generator, and a specific silicon compound, and has high resistance to peeling liquids, especially peeling liquid containing monoethanolamine, and NMP, The adhesiveness of is also good, the dry etching resistance is excellent, and the cured film which is hard to produce a display problem also in a display apparatus can be formed.

Moreover, it is preferable that the photosensitive resin composition of this invention is a chemically amplified positive photosensitive resin composition (chemical amplification positive photosensitive resin composition).

Moreover, the photosensitive resin composition of this invention can be used suitably as a positive photosensitive resin composition for dry etching resists.

In addition, in description of group (atom group) in this specification, the description which is not describing substitution and unsubstitution includes what has a substituent as well as not having a substituent. For example, an "alkyl group" includes not only the alkyl group (unsubstituted alkyl group) which does not have a substituent but the alkyl group (substituted alkyl group) which has a substituent.

In addition, the polymerization method may be sufficient as the method of introduce | transducing the structural unit contained in copolymers, such as the component A used for this invention, and a polymer reaction method may be sufficient as it. In the polymerization method, monomers containing a predetermined functional group are synthesized in advance, and these monomers are copolymerized. In the polymer reaction method, necessary functional groups are introduced into the structural units using the reactive groups contained in the structural units of the copolymer obtained after the polymerization reaction. The functional group is a crosslinkable group such as a protecting group, an epoxy group or an oxetanyl group, and an alkali such as a phenolic hydroxyl group or a carboxyl group, while protecting the acid group such as a carboxyl group or a phenolic hydroxyl group and decomposing in the presence of a strong acid. A soluble group (acid group) etc. can be illustrated.

<(A) polymer component>

The composition of the present invention is a polymer component comprising (1) a polymer having a structural unit having a moiety in which the (a1) acid group is protected with an acid decomposable group and (a2) a structural unit having a crosslinkable group and (2) an acid degradable acid group (a1) At least one of the polymer which has a structural unit which has group protected by the group, and the polymer which has a structural unit which has (a2) crosslinkable group is included. Moreover, polymers other than these may be included. (A) polymer component (Hereinafter, it may be called "(A) component") in this invention is another thing added as needed in addition to said (1) and / or (2) unless there is particular notice. It means that the polymer is included.

It is preferable that (A) component is addition polymerization type resin, and it is more preferable that it is a polymer containing the structural unit derived from (meth) acrylic acid and / or its ester. Moreover, you may have structural units other than the structural unit derived from (meth) acrylic acid and / or its ester, for example, the structural unit derived from styrene, the structural unit derived from a vinyl compound, etc.

In addition, "the structural unit derived from methacrylic acid and / or its ester" is also called "acrylic-type structural unit." In addition, "(meth) acrylic acid" shall mean "methacrylic acid and / or acrylic acid."

<< structural unit (a1) >>

Component A has at least the structural unit in which an acidic radical (a1) has the group protected by the acid-decomposable group. When (A) component has a structural unit (a1), it can be set as the very highly sensitive photosensitive resin composition.

"Group in which an acidic radical was protected by the acid-decomposable group" in this invention can use a well-known thing as an acidic radical and an acid-decomposable group, and is not specifically limited. As a specific acidic group, a carboxyl group and phenolic hydroxyl group are mentioned preferably. Moreover, as an acid-decomposable group, Acetal type, such as group which is comparatively easy to decompose | dissolve by an acid (for example, ester structure of group represented by Formula (A1) mentioned later, tetrahydropyranyl ester group, or tetrahydrofuranyl ester group) Functional groups) and groups (for example, tertiary alkyl groups such as tert-butyl ester groups, tert-butyl carbonate groups and tertiary alkyl carbonate groups such as tert-butyl ester groups) which can be relatively decomposed by an acid can be used.

The structural unit (a1) in which the acid group has a group protected with an acid decomposable group is preferably a structural unit having a protective carboxyl group protected with an acid decomposable group or a structural unit having a protected phenolic hydroxyl group protected with an acid decomposable group.

Hereinafter, the structural unit (a1-1) which has the protective carboxyl group protected by the acid-decomposable group, and the structural unit (a1-2) which has the protective phenolic hydroxyl group protected by the acid-decomposable group are demonstrated in order, respectively.

<<< structural unit which has protective carboxyl group protected by (a1-1) acid-decomposable group >>>

The structural unit (a1-1) which has the protective carboxyl group protected by the said acid-decomposable group is a structural unit which has the protective carboxyl group protected by the acid-decomposable group demonstrated in detail below.

As a structural unit which has the said carboxyl group which can be used for the structural unit (a1-1) which has a protective carboxyl group protected by the said acid-decomposable group, a well-known structural unit can be used without a restriction | limiting. For example, structural unit (a1-1-1) derived from unsaturated carboxylic acid etc. which have at least 1 carboxyl group in molecules, such as unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, and unsaturated tricarboxylic acid, etc., and ethylene The structural unit (a1-1-2) which has a structure derived from a unsaturated unsaturated group and an acid anhydride together is mentioned.

Hereinafter, the structural unit derived from unsaturated carboxylic acid etc. which have at least 1 carboxyl group in (a1-1-1) molecule | numerator used as a structural unit which has the said carboxyl group, (a1-1-2) ethylenically unsaturated group and acid anhydride The structural unit which has the derived structure together is demonstrated in order, respectively.

Structural unit >>>> derived from unsaturated carboxylic acid etc. which have at least 1 carboxyl group in <<<< (a1-1-1) molecule | numerator

As an unsaturated carboxylic acid used by this invention as a structural unit (a1-1-1) derived from the unsaturated carboxylic acid etc. which have at least 1 carboxyl group in the said molecule | numerator, what is enumerated below is used. That is, as unsaturated monocarboxylic acid, acrylic acid, methacrylic acid, crotonic acid, (alpha) -chloroacrylic acid, cinnamic acid, 2- (meth) acryloyloxyethyl- succinic acid, 2- (meth) acryloyloxyethyl, for example Hexahydrophthalic acid, 2- (meth) acryloyloxyethyl-phthalic acid, etc. are mentioned. In addition, examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, and the like. Moreover, the acid anhydride may be sufficient as unsaturated polyhydric carboxylic acid used in order to acquire the structural unit which has a carboxyl group. Specific examples thereof include maleic anhydride, itaconic anhydride, and citraconic anhydride. In addition, the unsaturated polyhydric carboxylic acid may be mono (2-methacryloyloxyalkyl) ester of polyhydric carboxylic acid, for example, succinic acid mono (2-acryloyloxyethyl) or succinic acid mono (2-methacryl). Monooxyethyl), mono (2-acryloyloxyethyl) phthalate, mono (2-methacryloyloxyethyl) phthalate, and the like. In addition, the unsaturated polyhydric carboxylic acid may be mono (meth) acrylate of the both terminal dicarboxy polymers, for example, omega-carboxypolycaprolactone monoacrylate, omega-carboxypolycaprolactone monomethacrylate, etc. may be mentioned. have. As the unsaturated carboxylic acid, acrylic acid-2-carboxyethyl ester, methacrylic acid-2-carboxyethyl ester, maleic acid monoalkyl ester, fumaric acid monoalkyl ester, 4-carboxystyrene and the like can also be used.

Especially, in order to form the structural unit (a1-1-1) derived from unsaturated carboxylic acid etc. which have at least 1 carboxyl group in the said molecule from a developable viewpoint, acrylic acid, methacrylic acid, 2- (meth) acryloyl It is preferable to use oxyethyl-succinic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid, 2- (meth) acryloyloxyethyl-phthalic acid or anhydrides of unsaturated polyhydric carboxylic acids, and the like. It is more preferable to use krylic acid and 2- (meth) acryloyloxyethyl hexahydrophthalic acid.

The structural unit (a1-1-1) derived from unsaturated carboxylic acid etc. which have at least 1 carboxyl group in the said molecule may be comprised individually by 1 type, and may be comprised by 2 or more types.

Structural unit >>>> which has a structure derived from <<<< (a1-1-2) ethylenically unsaturated group and acid anhydride

It is preferable that the structural unit (a1-1-2) which has a structure derived from an ethylenically unsaturated group and acid anhydride together is a unit derived from the monomer obtained by making the hydroxyl group and acid anhydride which exist in the structural unit which has an ethylenically unsaturated group react.

As said acid anhydride, a well-known thing can be used, Specifically, Dibasic acid anhydrides, such as maleic anhydride, succinic anhydride, itaconic acid anhydride, phthalic anhydride, tetrahydro phthalic anhydride, hexahydro phthalic anhydride, chloric anhydride; And acid anhydrides such as trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic acid anhydride, and biphenyltetracarboxylic acid anhydride. In these, phthalic anhydride, tetrahydro phthalic anhydride, or succinic anhydride is preferable from a developable viewpoint.

The reaction rate with respect to the hydroxyl group of the said acid anhydride becomes like this. Preferably it is 10-100 mol%, More preferably, it is 30-100 mol%.

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

The acid-decomposable group described above can be used as the acid-decomposable group that can be used in the structural unit (a1-1) having a protective carboxyl group protected with the acid-decomposable group.

Among these acid-decomposable groups, the carboxyl group is a protective carboxyl group protected in the form of acetal from the viewpoint of the basic physical properties of the photosensitive resin composition, in particular, the sensitivity and pattern shape, the formation of contact holes, and the storage stability of the photosensitive resin composition. Moreover, it is more preferable from a viewpoint of a sensitivity that a carboxyl group is a protective carboxyl group protected by the form of the acetal represented by following General formula (a1-10) among acid-decomposable groups. In addition, when the carboxyl group is a protected carboxyl group protected in the form of acetal represented by the following general formula (a1-10), the whole of the protected carboxyl group has a structure of-(C = O) -O-CR ¹⁰¹ R ¹⁰² (OR ¹⁰³ ). It is.

General formula (a1-10)

(In formula (a1-10), R ¹⁰¹ and R ¹⁰² each independently represent a hydrogen atom or an alkyl group, except that R ¹⁰¹ and R ¹⁰² together represent a hydrogen atom. R ¹⁰³ represents an alkyl group. R ¹⁰¹ or R ¹⁰² and R ¹⁰³ may be linked to each other to form a cyclic ether)

In said general formula (a1-10), R <^101> -R <^103> respectively independently represents a hydrogen atom or an alkyl group, and the said alkyl group may be any of linear, branched, and cyclic. Both 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.

In the general formula (a1-10), when R ¹⁰¹ , R ¹⁰² and R ¹⁰³ represent an alkyl group, the alkyl group may be linear, branched or cyclic.

As said linear or branched alkyl group, it is preferable that it is C1-C12, It is more preferable that it is C1-C6, It is further more preferable that it is C1-C4. Specifically, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, n-hexyl group , Texyl group (2,3-dimethyl-2-butyl group), n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, etc. are mentioned.

As said cyclic alkyl group, C3-C12 is preferable, C4-C8 is more preferable, C4-C6 is further more preferable. As said cyclic alkyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, isobonyl group etc. are mentioned, for example.

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

As said halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom can be illustrated, Among these, a fluorine atom or a chlorine atom is preferable.

Moreover, as said aryl group, a C6-C20 aryl group is preferable, More preferably, it is C6-C12, Specifically, a phenyl group, (alpha) -methylphenyl group, a naphthyl group, etc. can be illustrated, and is substituted by the aryl group. As a whole alkyl group, ie, an aralkyl group, a benzyl group, (alpha)-methyl benzyl group, a phenethyl group, a naphthyl methyl group, etc. can be illustrated.

As said alkoxy group, a C1-C6 alkoxy group is preferable, More preferably, it is C1-C4, A methoxy group or an ethoxy group is more preferable.

In addition, when the said alkyl group is a cyclic alkyl group, the said cyclic alkyl group may have a C1-C10 linear or branched alkyl group as a substituent, and when a alkyl group is a linear or branched alkyl group, it is C3 as a substituent. You may have a ~ 12 cyclic alkyl group.

These substituents may further be substituted by the said substituent.

When R ¹⁰¹ , R ¹⁰² and R ^{103 in} the general formula (a1-10) represent an aryl group, the aryl group is preferably 6 to 12 carbon atoms, and more preferably 6 to 10 carbon atoms. The said aryl group may have a substituent and can preferably illustrate a C1-C6 alkyl group as said substituent. As an aryl group, a phenyl group, a tril group, cumenyl group, 1-naphthyl group etc. can be illustrated, for example.

In addition, R ¹⁰¹ , R ¹⁰² and R ¹⁰³ may be bonded to each other to form a ring together with the carbon atom 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 combine with each other include cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, tetrahydrofuranyl group, and And a dantilyl group and a tetrahydropyranyl group.

In formula (a1-10), one of R ¹⁰¹ and R ¹⁰² is preferably a hydrogen atom or a methyl group.

A commercially available radical may be used for the radically polymerizable monomer used in order to form the structural unit which has a protective carboxyl group represented by said general formula (a1-10), and what synthesize | combined by a well-known method can also be used. For example, Paragraph No. 0037 of Unexamined-Japanese-Patent No. 2011-221494-the synthesis method of 0040 can be synthesize | combined.

The 1st preferable embodiment of the structural unit (a1-1) which has the protective carboxyl group protected by the said acid-decomposable group is a structural unit represented with the following general formula.

(Wherein R ¹ and R ² each represent a hydrogen atom, an alkyl group or an aryl group, at least one of R ¹ and R ² is an alkyl group or an aryl group, R ³ represents an alkyl group or an aryl group, and R ¹ or R ² and R ³ may be linked 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> is an alkyl group, a C1-C10 alkyl group is preferable. Phenyl groups are preferred when R ¹ and R ² are aryl groups. R ¹ and R ² are each preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

R <^3> represents an alkyl group or an aryl group, a C1-C10 alkyl group is preferable and 1-6 alkyl group is more preferable.

X represents a single bond or an arylene group, and a single bond is preferable.

2nd preferable embodiment of the structural unit (a1-1) which has the protective carboxyl group protected by the said acid-decomposable group is a structural unit of the following general formula.

(In the formula, 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 hydrogen atoms.

The following structural unit can be illustrated as a preferable specific example of structural unit (a1-1) which has the protective carboxyl group protected by the said acid-decomposable group. R represents a hydrogen atom or a methyl group.

<<< structural unit which has protective phenolic hydroxyl group protected by the (a1-2) acid-decomposable group >>>

The structural unit (a1-2) which has the protective phenolic hydroxyl group protected by the said acid-decomposable group is a structural unit which has a protective phenolic hydroxyl group by the acid-decomposable group which the structural unit which has a phenolic hydroxyl group demonstrates in detail below.

Structural unit >>>> which has <<<< (a1-2-1) phenolic hydroxyl group

As a structural unit which has the said phenolic hydroxyl group, the structural unit in a hydroxy styrene-type structural unit and novolak-type resin is mentioned, Among these, the structural unit derived from hydroxy styrene or (alpha) -methylhydroxy styrene is sensitive. It is preferable from a viewpoint. Moreover, the structural unit represented by the following general formula (a1-20) as a structural unit which has a phenolic hydroxyl group is also preferable from a viewpoint of a sensitivity.

General formula (a1-20)

(In general formula (a1-20), 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, and when R ²²² is 2 or more, these R ²²² may be different or the same)

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

In addition, R ²²¹ represents a single bond or a divalent linking group. In the case of a single bond, since sensitivity can be improved and transparency of a cured film can be improved further, it is preferable. Examples of the divalent linking group for R ²²¹ include an alkylene group, and specific examples in which 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, a tert-butylene group, Pentylene group, isopentylene group, neopentylene group, hexylene group, etc. are mentioned. Especially, it is preferable that R <^221> is a single bond, a methylene group, and an ethylene group. The divalent linking group may have a substituent, and examples of the substituent include a halogen atom, a hydroxyl group, and an alkoxy group. In addition, although a shows the integer of 1-5, it is preferable that a is 1 or 2 from a viewpoint of the effect of this invention and manufacture, and it is more preferable that a is 1.

In addition, it is preferable that the coupling | bonding position of the hydroxyl group in a benzene ring couple | bonds in 4 positions, when the carbon atom couple | bonded with R <^221> is a reference | standard (1 position).

R ²²² is a halogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms. Specifically, a fluorine atom, a chlorine atom, a bromine atom, a methyl group, an ethyl group, a propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, etc. are mentioned. Can be. Among them, chlorine atom, bromine atom, methyl group or ethyl group is preferable from the viewpoint of easy production.

In addition, b represents the integer of 0 or 1-4.

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

As said acid-decomposable group which can be used for the structural unit (a1-2) which has the protective phenolic hydroxyl group protected by the said acid-decomposable group, the said acid usable group can be used for the structural unit (a1-1) which has the protective carboxyl group protected by the said acid-decomposable group. A well-known thing can be used similarly to an acid-decomposable group, and is not specifically limited. Among the acid decomposable groups, a structural unit having a protective phenolic hydroxyl group protected with acetal is preferable from the viewpoint of the basic physical properties of the photosensitive resin composition, in particular, the sensitivity and pattern shape, the storage stability of the photosensitive resin composition, and the formability of the contact hole. Moreover, it is more preferable from a viewpoint of a sensitivity that a phenolic hydroxyl group is a protected phenolic hydroxyl group protected by the form of the acetal represented by said general formula (a1-10) among acid-decomposable groups. Further, in the phenolic hydroxyl groups when the above-mentioned general formula (a1-10) protected phenolic hydroxyl date protection in the form of an acetal represented by as a whole of the protected phenolic hydroxyl group ^{-Ar-O-CR 101 R 102} (OR 103) It is structured. Ar represents an arylene group.

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

Moreover, as a radically polymerizable monomer used in order to form the structural unit which has a protective phenolic hydroxyl group in which a phenolic hydroxyl group was protected by the form of acetal, what was described, for example in Paragraph No. 0042 of Unexamined-Japanese-Patent No. 2011-215590, etc. Can be mentioned.

Among these, the 1-alkoxyalkyl protecting body of 4-hydroxyphenyl methacrylate and the tetrahydropyranyl protecting body of 4-hydroxyphenyl methacrylate are preferable from the viewpoint of transparency.

As a specific example of the acetal protecting group of a phenolic hydroxyl group, 1-alkoxyalkyl group is mentioned, For example, 1-ethoxyethyl group, 1-methoxyethyl group, 1-n-butoxyethyl group, 1-isobutoxyethyl group, 1- ( 2-chloroethoxy) ethyl group, 1- (2-ethylhexyloxy) ethyl group, 1-n-propoxyethyl group, 1-cyclohexyloxyethyl group, 1- (2-cyclohexylethoxy) ethyl group, 1-benzyl An oxyethyl group etc. are mentioned, These can be used individually or in combination of 2 or more types.

The radically polymerizable monomer used in order to form the structural unit (a1-2) which has the protective phenolic hydroxyl group protected by the said acid-decomposable group may use a commercially available thing, and may use the thing by a well-known method. For example, it can synthesize | combine the compound which has a phenolic hydroxyl group by reacting with vinyl ether in presence of an acidic catalyst. Said synthesis | combination may copolymerize previously the monomer which has a phenolic hydroxyl group with another monomer, and may make it react with vinyl ether in presence of an acidic catalyst after that.

Although the following structural unit can be illustrated as a preferable specific example of structural unit (a1-2) which has the protective phenolic hydroxyl group protected by the said acid-decomposable group, this invention is not limited to these.

<<< preferred embodiment of a structural unit (a1) >>>

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

When the polymer containing the structural unit (a1) contains the following structural unit (a2), the single structural unit (a1) is 3 from the viewpoint of sensitivity among the polymers containing the structural unit (a1) and the structural unit (a2). -70 mol% is preferable and 10-60 mol% is more preferable. Moreover, 20-50 mol% is preferable especially when the said acid-decomposable group which can be used for the said structural unit (a1) is a structural unit which has the protective carboxyl group in which the carboxyl group was protected by the form of acetal.

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

<< structural unit which has a (a2) crosslinkable group >>

(A) component has a structural unit (a2) which has a crosslinkable group. The crosslinkable group is not particularly limited as long as it is a group causing a curing reaction by heat treatment. At least one selected from the group consisting of an epoxy group, an oxetanyl group, a group represented by -NH-CH ₂ -OR (R is an alkyl group having 1 to 20 carbon atoms) and an ethylenically unsaturated group as an embodiment of a structural unit having a preferred crosslinkable group there may be mentioned a structural unit, an epoxy group, an oxetanyl group and the -NH-CH ₂ -OR containing preferably at least one selected from the groups represented by (R is an alkyl group having 1 to 20 carbon atoms). Especially, it is preferable that the photosensitive resin composition of this invention contains the structural unit in which the said (A) component contains at least 1 of an epoxy group and an oxetanyl group. In more detail, the following are mentioned.

<< structural unit which has a (a2-1) epoxy group and / or oxetanyl group >>>

It is preferable that the said (A) polymer contains the structural unit (structural unit (a2-1)) which has an epoxy group and / or an oxetanyl group. The said 3-membered ring cyclic ether group is also called an epoxy group, and a 4-membered ring cyclic ether group is also called an oxetanyl group.

The structural unit (a2-1) which has the said epoxy group and / or oxetanyl group should just have at least 1 epoxy group or oxetanyl group in one structural unit, and at least 1 epoxy group and 1 or more oxetanyl group, two Although it may have the above epoxy group or two or more oxetanyl groups, although it is not specifically limited, It is preferable to have 1-3 epoxy groups and / or oxetanyl groups in total, and it has one or two epoxy groups and / or oxetanyl groups in total. It is more preferable, and it is still more preferable to have one epoxy group or oxetanyl group.

As a specific example of the radically polymerizable monomer used in order to form the structural unit which has an epoxy group, glycidyl acrylate, glycidyl methacrylate, the glycidyl (alpha)-ethyl acrylate, the glycidyl (alpha)-n-propyl acrylate, for example. , α-n-butyl acrylate glycidyl, acrylic acid-3,4-epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-3,4-epoxycyclohexylmethyl, methacrylic acid-3,4- Epoxycyclohexylmethyl, α-ethylacrylic acid-3,4-epoxycyclohexylmethyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, Japanese Patent No. 4168443 The compound containing the alicyclic epoxy skeleton of Paragraph No. 0031-0035 of Unexamined-Japanese-Patents, etc. are mentioned, The content of these is contained in this specification.

As a specific example of the radically polymerizable monomer used in order to form the structural unit which has an oxetanyl group, (meth) acrylic acid ester etc. which have the oxetanyl group of Paragraph No. 0011-0016 of Unexamined-Japanese-Patent No. 2001-330953, etc. are mentioned, for example. The contents thereof are included in the specification.

As a specific example of the radically polymerizable monomer used in order to form the structural unit (a2-1) which has the said epoxy group and / or oxetanyl group, it is preferable that it is a monomer containing a methacrylic ester structure, and a monomer containing an acrylic ester structure. Do.

Among these, preferred are methacrylic acid glycidyl, acrylic acid 3,4-epoxycyclohexylmethyl, methacrylic acid 3,4-epoxycyclohexylmethyl, acrylic acid (3-ethyloxetan-3-yl) methyl and methacrylic acid (3-ethyloxetan-3-yl) methyl. These structural units can be used individually by 1 type or in combination of 2 or more types.

The following structural unit can be illustrated as a preferable specific example of structural unit (a2-1) which has the said epoxy group and / or oxetanyl group. R represents a hydrogen atom or a methyl group.

<<< structural unit which has (a2-2) ethylenically unsaturated group >>>

The structural unit (a2-2) which has an ethylenically unsaturated group is mentioned as one of the structural units (a2) which have the said crosslinkable group (henceforth "a structural unit (a2-2)"). As a structural unit (a2-2) which has the said ethylenically unsaturated group, the structural unit which has an ethylenically unsaturated group in a side chain is preferable, The structural unit which has an ethylenically unsaturated group at the terminal, and has a C3-C16 side chain, The structural unit which has a side chain represented by the following general formula (a2-2-1) is more preferable.

General formula (a2-2-1)

(In formula (a2-2-1), R ³⁰¹ represents a divalent linking group having 1 to 13 carbon atoms, R ³⁰² represents a hydrogen atom or a methyl group, and * is connected to the main chain of the structural unit (a2) having a crosslinkable group.) I show a part to say)

R ³⁰¹ is a C1-C13 divalent linking group, which includes an alkenyl 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. In addition, the divalent linking group may have substituents, such as a hydroxyl group and a carboxyl group, in arbitrary positions. Specific examples of R ³⁰¹ include the following divalent linking groups.

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

In addition, about the structural unit which has (a2-2) ethylenically unsaturated group, Paragraph No. 0072 of Unexamined-Japanese-Patent No. 2011-215580-description of 0090 can be considered into consideration, and the content is included in this specification.

_{<<< (a2-3) -NH-CH 2} -OR configuration having a group represented by (R is an alkyl group having 1 to 20 carbon atoms) unit >>>

Polymer used in the present invention is -NH-CH ₂ -OR is also preferred structural units (a2-3) having a group represented by (R is an alkyl group having 1 to 20 carbon atoms). By having a structural unit (a2-3), hardening reaction can be raised by smooth heat processing and the cured film excellent in various characteristics can be obtained. R is preferably an alkyl group having 1 to 9 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. The alkyl group may be any of a linear, branched or cyclic alkyl group, but is preferably a linear or branched alkyl group. Structural unit (a2), It is a structural unit which, more preferably, has group represented by the following general formula (a2-30).

General formula (a2-30)

(In general formula (a2-30), R <^1> represents a hydrogen atom or a methyl group, and R <^2> represents a C1-C20 alkyl group.)

R ² 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 a linear, branched or cyclic alkyl group, but is preferably a linear or branched alkyl group.

As a specific example of R <^2> , a methyl group, an ethyl group, n-butyl group, i-butyl group, a cyclohexyl group, and n-hexyl group are mentioned. Especially, i-butyl group, n-butyl group, and a methyl group are preferable.

<<< preferred embodiment of a structural unit (a2) >>>

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

When the polymer containing the structural unit (a2) contains the structural unit (a1), the single structural unit (a2) is selected from the viewpoint of drug resistance among the polymers containing the structural unit (a1) and the structural unit (a2). 3-70 mol% is preferable and 10-60 mol% is more preferable.

In this invention, it is preferable to contain 3-70 mol% of structural units (a2) among all the structural units of (A) component further, and, as for any embodiment, it is more preferable to contain 10-60 mol%.

If it is in the range of said numerical value, transparency and chemical resistance of the cured film obtained from the photosensitive resin composition will become favorable.

<< (a3) other structural units >>

In this invention, (A) component may have other structural units (a3) other than these in addition to the said structural unit (a1) and / or (a2). These structural units may contain the said polymer component (1) and / or (2). Moreover, you may have a polymer component which does not contain (a1) and (a2) substantially, and has another structural unit (a3) separately from the said polymer component (1) or (2). When the polymer component including (a1) and (a2) substantially does not include (a1) and (a2) separately from the polymer component (1) or (2) and includes another structural unit (a3), the blending amount of the polymer component is 60% of the total polymer component. It is preferable that it is mass% or less, It is more preferable that it is 40 mass% or less, It is further more preferable that it is 20 mass% or less.

There is no restriction | limiting in particular as a monomer used as another structural unit (a3), For example, styrene, (meth) acrylic-acid alkylester, (meth) acrylic-acid cyclic alkylester, (meth) acrylic-acid arylester, unsaturated dicarboxylic acid diester And bicyclo unsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated dicarboxylic anhydrides, and other unsaturated compounds. Moreover, you may have a structural unit which has an acidic radical as mentioned later. The monomer used as another structural unit (a3) can be used individually or in combination of 2 or more types.

Although the preferred embodiment of the polymer component of this invention is given to the following, this invention is not limited to these.

(First Embodiment)

Embodiment in which the polymer component (1) further has 1 type, or 2 or more types of other structural unit (a3).

(Second Embodiment)

Embodiment in which the polymer which has a structural unit in which the acidic radical (a1) of the polymer component (2) has group protected by the acid-decomposable group further has 1 type, or 2 or more types of other structural unit (a3).

(Third Embodiment)

Embodiment in which the polymer which has a structural unit which has a (a2) crosslinkable group of the polymer component (2) further has 1 type, or 2 or more types of other structural unit (a3).

(Fourth Embodiment)

Embodiment in any one of said 1st-3rd embodiment containing the structural unit which contains an acidic radical at least as other structural unit (a3).

(Fifth Embodiment)

An embodiment having a polymer which, apart from the polymer component (1) or (2), is substantially free of (a1) and (a2) and further has other structural units (a3).

(Sixth Embodiment)

An embodiment comprising at least a polymer component (2).

(Seventh Embodiment)

Embodiment which consists of two or more combinations of the said, 1st-6th embodiment.

(Eighth embodiment)

Embodiment containing the polymer which has a structural unit which has an acidic radical at least as another structural unit (a3) separately from the said polymeric component (1) or (2).

(Ninth embodiment)

Embodiment including the copolymer which has a structural unit which has an acidic radical, and a structural unit which has a crosslinkable group at least as another structural unit (a3) separately from the said polymeric component (1) or (2).

(10th embodiment)

Embodiment in the said Embodiment 8 or 9 whose acid group is a structural unit which has a carboxyl group and / or a phenolic hydroxyl group.

The structural unit (a3) is specifically styrene, tert-butoxystyrene, methyl styrene, hydroxy styrene, α-methyl styrene, acetoxy styrene, methoxy styrene, ethoxy styrene, chloro styrene, methyl vinyl benzoate, vinyl benzoic acid Ethyl, 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, acrylonitrile, ethylene glycol monoacetoacetate monomethacrylate and the like A unit is mentioned. In addition, Paragraph No. 0021 of Unexamined-Japanese-Patent No. 2004-264623-the compound of 0024 can be mentioned.

Moreover, the group which has styrene and an alicyclic skeleton as other structural unit (a3) is preferable from a viewpoint of an electrical property. Specifically, styrene, tert-butoxy styrene, methyl styrene, hydroxy styrene, α-methyl styrene, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, benzyl ( Meth) acrylate, etc. are mentioned.

Moreover, (meth) acrylic-acid alkylester is preferable from a viewpoint of adhesiveness as other structural unit (a3). Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, etc. are mentioned, and methyl (meth) acrylate is more preferable. 60 mol% or less is preferable, as for the content rate of the said structural unit (a3) among the structural units which comprise a polymer (A), 50 mol% or less is more preferable, 40 mol% or less is more preferable. As a lower limit, although 0 mol% may be sufficient, for example, it can be 1 mol% or more, and can also be 5 mol% or more. If it exists in the range of the said numerical value, the various characteristics of the cured film obtained from the photosensitive resin composition will become favorable.

  It is preferable to contain an acidic radical as another structural unit (a3). By including an acid group, it becomes easy to melt | dissolve in an alkaline developing solution, and the effect of this invention is exhibited more effectively. The acidic radical in this invention means a proton dissociable group whose pKa is smaller than seven. An acidic radical is contained in a polymer as a structural unit containing an acidic radical using the monomer which can form an acidic radical normally. It exists in the tendency to become easy to melt | dissolve with respect to an alkaline developing solution, by including in a polymer the structural unit containing such an acidic radical.

The acid groups used in the present invention include those derived from carboxylic acid groups, those derived from sulfonamide groups, those derived from phosphonic acid groups, those derived from sulfonic acid groups, those derived from phenolic hydroxyl groups, sulfonamide groups, Sulfonyl imide groups etc. are illustrated and it is preferable to derive from a carboxylic acid group and / or derived from a phenolic hydroxyl group.

As a radically polymerizable monomer used in order to form the structural unit which has a carboxyl group, For example, Monocarboxylic acids, such as acrylic acid, methacrylic acid, a crotonic acid; Unsaturated carboxylic acids, such as dicarboxylic acid, such as maleic acid, a fumaric acid, a citraconic acid, a mesaconic acid, and itaconic acid, are mentioned as a preferable thing.

Moreover, as a radically polymerizable monomer used in order to form the structural unit which has a carboxylic anhydride residue, maleic anhydride, itaconic anhydride, etc. are mentioned as a preferable thing, for example.

As a radically polymerizable monomer used in order to form the structural unit which has a phenolic hydroxyl group, For example, hydroxystyrenes, such as p-hydroxy styrene and (alpha) -methyl- p-hydroxy styrene, Unexamined-Japanese-Patent No. 2008-40183 Compounds described in paragraphs 0011 to 0016 of the publication, 4-hydroxybenzoic acid derivatives described in paragraphs 0007 to 0010 of Japanese Patent No. 2888454, addition reactants of 4-hydroxybenzoic acid and glycidyl methacrylate, 4-hydride Addition reaction products of oxybenzoic acid and glycidyl acrylate etc. are mentioned as a preferable thing.

Among these, methacrylic acid, acrylic acid, the compound of Paragraph 0011-0016 of Unexamined-Japanese-Patent No. 2008-40183, the 4-hydroxy benzoic acid derivatives of Paragraph 0007-0010 of Unexamined-Japanese-Patent No. 2888454, 4-hydroxy The addition reactant of benzoic acid and glycidyl methacrylate, and the addition reactant of 4-hydroxybenzoic acid and glycidyl acrylate are more preferable, and the compounds described in paragraphs 0011 to 0016 of JP2008-40183A, Japanese Patent No. The 4-hydroxybenzoic acid derivatives described in paragraphs 0007 to 0010 of Publication No. 2888454, addition reactants of 4-hydroxybenzoic acid and methacrylic acid glycidyl, addition reactants of 4-hydroxybenzoic acid and glycidyl acrylate are preferable. And structural units derived from at least one member selected from the group consisting of acrylic acid, methacrylic acid, p-hydroxystyrene and α-methyl-p-hydroxystyrene. It is more preferable, It is still more preferable that it is a structural unit derived from acrylic acid or methacrylic acid, It is especially preferable that it is a structural unit derived from methacrylic acid. These structural units can be used individually by 1 type or in combination of 2 or more types.

As a preferable specific example of structural unit (b1), the following structural unit can be illustrated.

As for the structural unit containing an acidic radical, 1-80 mol% of the structural unit of all the polymer components is preferable, 1-50 mol% is more preferable, 5-40 mol% is still more preferable, 5-30 mol% is especially It is preferable and 5-20 mol% is especially preferable.

In this invention, resin which has a carboxyl group in a side chain is preferable as a polymer which does not contain (a1) and (a2) substantially, and has another structural unit (a3) separately from the said polymer component (1) or (2). For example, Japanese Patent Publication No. 59-44615, Japanese Patent Publication 54-34327, Japanese Patent Publication 58-12577, Japanese Patent Publication 54-25957, Japanese Patent Publication 59-53836, Japan Methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers and the like described in each publication of Japanese Patent Application Laid-Open No. 59-71048 And an acid anhydride added to a polymer having an acidic cellulose derivative having a hydroxyl group, and the like, and a polymer polymer having a (meth) acryloyl group in its side chain may also be mentioned as a preferable one.

For example, benzyl (meth) acrylate / (meth) acrylic acid copolymer, 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, Japanese Patent Laid-Open No. 7-140654 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer described in Japanese Patent Publication No. / 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 Laid-Open No. 7-207211, Japanese Patent Laid-Open No. 8-259876, Japanese Patent Laid-Open No. 10-300922, Japanese Patent Laid-Open No. 11-140144, Japanese Patent Laid-Open No. 11-174224 The well-known high molecular compound of Unexamined-Japanese-Patent No. 2000-56118, Unexamined-Japanese-Patent No. 2003-233179, Unexamined-Japanese-Patent No. 2009-52020, etc. can be used, The content is contained in this specification.

One type of these polymers may be included and they may be included two or more types.

Commercially available polymers such as SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P, SMA 3840F (manufactured by Satomer), ArUFON UC-3000, ArUFON UC-3510, ArUFON UC-3900, ArUFON UC-3910, ArUFON UC-3920, ArUFON UC-3080 (above manufactured by Toagosei Co., Ltd.), Joncryl 690, Joncryl 678, Joncryl 67, Joncryl 586 (above BASF), etc. can also be used.

When using styrene, such as styrene and (alpha) -methylstyrene, as another structural unit (a3), it is preferable to further have a structural unit represented by following formula (b3-1). R ⁴ is preferably a hydrogen atom.

(Wherein R ⁴ represents a hydrogen atom or a methyl group)

Moreover, as an example of a structural unit (b3), the structural unit derived from at least 1 sort (s) chosen from the group which consists of (meth) acrylic acid ester, styrene, and N-substituted maleimide is mentioned preferably, (meth) acrylic acid ester And structural units derived from at least one selected from the group consisting of styrenes.

Especially, as a radically polymerizable monomer used in order to form a structural unit (b3), the (meth) acrylic acid ester which has alicyclic structure, such as (meth) acrylic-acid dicyclopentanyl, (meth) acrylic acid cyclohexyl, and cyclohexyl acrylate, ( Methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and styrene can be illustrated preferably, Methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and styrene can be illustrated more preferably, Methyl (meth) acrylate can be illustrated more preferably, and methyl methacrylate can be illustrated especially preferably.

<< molecular weight of (A) polymer >>

The molecular weight of the polymer (A) is preferably in the range of 1,000 to 200,000, more preferably 2,000 to 50,000 in terms of the polystyrene reduced weight average molecular weight. Various characteristics are favorable as it exists in the range of the said numerical value. 1.0-5.0 are preferable and, as for ratio (dispersion degree) of a number average molecular weight and a weight average molecular weight, 1.5-3.5 are more preferable.

<< (A) manufacturing method of polymer >>

Moreover, although various methods are known also about the synthesis | combining method of (A) component, For example, radically polymerizable including the radically polymerizable monomer used in order to form the structural unit represented by said (a1) and said (a3) at least. A monomer mixture can be synthesize | combined by superposing | polymerizing using the radical polymerization initiator in the organic solvent. Moreover, it can also synthesize | combine by what is called a polymer reaction.

It is preferable to contain (A) component in the ratio of 50-99.9 mass parts with respect to 100 mass parts of total solids, and, as for the photosensitive resin composition of this invention, it is more preferable to contain in 70-98 mass parts.

<Component (X)>

The silicon compound used in the present invention is characterized by having two or more hydrolyzable silyl groups and / or silanol groups represented by the following formula (X1) in one molecule.

^Wherein at least one of R ^X1 to R ^X3 is a hydrolyzable group selected from the group consisting of an alkoxy group, a mercapto group, a halogen atom, an amide group, an acetoxy group, an amino group, an allyloxy group and an isopropenoxy group or Hydroxy group, and the remaining R ^X1 to R ^X3 each independently represent a hydrogen atom, a halogen atom or a monovalent organic substituent)

At least one of R ^X1 to R ^X3 in formula (X1) is hydrolyzed selected from the group consisting of an alkoxy group, mercapto group, halogen atom, amide group, acetoxy group, amino group, allyloxy group and isopropenoxy group It represents a genital group or a hydroxyl group. The remaining R ^X1 to R ^X3 each independently represent a hydrogen atom, a halogen atom or a monovalent organic substituent (eg, an alkyl group, an aryl group, an alkenyl group, an alkynyl group, an aralkyl group).

As a hydrolyzable group couple | bonded with a silicon atom in Formula (X1), an alkoxy group and a halogen atom are especially preferable, and an alkoxy group is more preferable.

As an alkoxy group, a C1-C30 alkoxy group is preferable from a viewpoint of a rinse property and a chain resistance, A C1-C15 alkoxy group is more preferable, A C1-C5 alkoxy group is more preferable, A C1-C3 alkoxy group is further more preferable. It is preferable and a methoxy group or an ethoxy group is especially preferable.

Examples of the halogen atom include F atom, Cl atom, Br atom, and I atom. From the viewpoint of ease of synthesis and stability, Cl atom and Br atom are preferable, and Cl atom is more preferable. Can be.

Component X has two or more groups represented by formula (X1). That is, the compound which has two or more silicon atoms which the hydrolysable group couple | bonded in the molecule | numerator is used preferably. 2-6 are preferable, as for the number of the silicon atoms which the hydrolyzable group contained in the component A couple | bonded, 2-4 are more preferable, and 2 or 3 are still more preferable.

By having two or more structural component (X1), it can function as a crosslinking agent in a cured film, and can improve the resistance to the peeling liquid and a solvent of a cured film.

The hydrolyzable group can be bonded to one silicon atom in the range of 1 to 4, and the total number of hydrolyzable groups in the formula (X1) is preferably in the range of 2 or 3, and the three hydrolyzable groups It is especially preferable to combine. When two or more hydrolyzable groups couple | bond with a silicon atom, they may mutually be same or different.

Preferred alkoxy groups as the hydrolyzable group include methoxy, ethoxy, propoxy, isopropoxy, butoxy, tert-butoxy, phenoxy and benzyloxy groups. A plurality of these alkoxy groups may be used in combination, or a plurality of other alkoxy groups may be used in combination.

As an alkoxy silyl group which the alkoxy group couple | bonded, For example, Trialkoxy silyl groups, such as a trimethoxy silyl group, a triethoxy silyl group, a triisopropoxy silyl group, and a triphenoxy silyl group; Dialkoxymonoalkylsilyl groups such as dimethoxymethylsilyl group and diethoxymethylsilyl group; Monoalkoxy dialkyl silyl groups, such as a methoxy dimethyl silyl group and an ethoxy dimethyl silyl group, are mentioned.

Component X may contain a sulfur atom, an ester bond, a urethane bond, an ether bond, a urea bond or an imino group. Especially, it is preferable that component X contains a sulfur atom from a crosslinking viewpoint, and also the ester bond, a urethane bond, or an ether bond (especially the ether bond contained in an oxyalkylene group) which is easy to decompose | disassemble into alkaline water from an alkali developability viewpoint. It is preferable to contain. The component X containing a sulfur atom may function as a vulcanizing agent, and may accelerate reaction (crosslinking) of a cured film. Moreover, it is preferable that component X in this invention is a compound which does not have an ethylenically unsaturated bond. It is preferable that component X has only hydrolyzable silyl group and / or silanol group as a polymerizable group.

Examples of the component X in the present invention include compounds in which the groups represented by the plurality of formulas (X1) are bonded via a divalent linking group. Examples of the divalent linking group include a sulfide group (-S-) from the viewpoint of the effect. And a linking group having an imino group (-N (R)-) or a urethane bond (-OCON (R)-or N (R) COO-). In addition, R represents a hydrogen atom or a substituent. As a substituent in R, an alkyl group, an aryl group, an alkenyl group, an alkynyl group, or an aralkyl group can be illustrated.

There is no restriction | limiting in particular as a synthesis | combining method of component X, It can synthesize | combine by a well-known method. As an example, a representative method for synthesizing component X including a linking group having the specific structure is shown.

<Synthesis method of a compound which has a sulfide group as a linking group, and also has a hydrolyzable silyl group and / or silanol group>

Although the synthesis | combining method of the component X which has a sulfide group as a coupling group (henceforth "a sulfide coupling group containing component X" suitably) is not specifically limited, Specifically, for example, reaction of the component X which has a halogenated hydrocarbon group, and alkali sulfide, a mercapto group Reaction of component X with a halogenated hydrocarbon, component X with a mercapto group and component X with a halogenated hydrocarbon group, reaction of component X with a halogenated hydrocarbon group and mercaptans, component X with an ethylenically unsaturated bond Reaction of captans, reaction of component X having an ethylenically unsaturated bond with component mercapto group, reaction of component having ethylenically unsaturated bond with component X having mercapto group, component having ketones and mercapto group Reaction of X, reaction of diazonium salt with component X having a mercapto group, reaction of component X having a mercapto group with oxiranes, The synthesis | combining method, such as reaction of the component X which has a lecapto group, the component X which has an oxirane group, reaction of the mercaptans and the component X which has an oxirane group, reaction of the component X which has a mercapto group, and aziridine etc. can be illustrated.

<Synthesis method of a compound which has an imino group as a coupling group, and also has a hydrolyzable silyl group and / or silanol group>

Although the synthesis | combining method of the component X which has an imino group as a coupling group (henceforth "imino coupling group containing component X" suitably) is not specifically limited, For example, reaction of the component X which has an amino group, and halogenated hydrocarbon, the component X which has an amino group, and halogenation Reaction of component X having a hydrocarbon group, reaction of component X having a halogenated hydrocarbon group with amines, reaction of component X having an amino group with oxiranes, reaction of component X having an amino group with component X having an oxysilane group, component having an amine and an oxysilane group Reaction of X, component X having an amino group and aziridines, reaction of component X having an ethylenically unsaturated bond with amines, reaction of component X having an ethylenically unsaturated bond with component X having an amino group, ethylenically unsaturated bond Reaction of a compound having a compound with an amino group with a compound having an acetylenically unsaturated bond; Reaction of component X having an amino group, reaction of component X having an imineically unsaturated bond with an organic alkali metal compound, reaction of component X having an imine unsaturated bond with an organic alkaline earth metal compound and reaction of component X having a carbonyl compound with an amino group Synthetic methods, such as these, can be illustrated.

<Synthesis method of a compound which has a urethane bond (ureylene group) as a coupling group, and also has a hydrolyzable silyl group and / or silanol group>

Although the synthesis | combining method of the component X (henceforth "the ureylene coupling group containing component X" suitably hereafter) as a coupling group is not specifically limited, For example, reaction of the component X which has an amino group, and isocyanate ester, and an amino group Synthetic methods, such as reaction of the component X which has a component X, and the component X which has an isocyanate ester, and the reaction of the amines and the component X which has an isocyanic acid ester, can be illustrated.

Specific examples of component X include 1,2-bis (triethoxysilyl) ethane, 1,4-bis (trimethoxysilyl) butane, 1-methyldimethoxysilyl-4-trimethoxysilylbutane, 1,4- Bis (methyldimethoxysilyl) butane, 1,5-bis (trimethoxysilyl) pentane, 1,4-bis (trimethoxysilyl) pentane, 1-methyldimethoxysilyl-5-trimethoxysilylpentane, 1,5-bis (methyldimethoxysilyl) pentane, 1,6-bis (trimethoxysilyl) hexane, 1,4-bis (trimethoxysilyl) hexane, 1,5-bis (trimethoxysilyl) Hexane, 2,5-bis (trimethoxysilyl) hexane, 1,6-bis (methyldimethoxysilyl) hexane, 1,7-bis (trimethoxysilyl) heptane, 2,5-bis (trimethoxy Silyl) heptane, 2,6-bis (trimethoxysilyl) heptane, 1,8-bis (trimethoxysilyl) octane, 2,5-bis (trimethoxysilyl) octane, 2,7-bis (tri Methoxysilyl) octane, 1,9-bis (trimethoxysilyl) nonane, 2,7-bis (trimethoxysilyl) nonane, 1,10-bis (trimethoxysilyl) decane, 3,8-bis (Trimethock Cylyl) decane, vinyltrichlorosilane, 1,3-bis (trichlorosilane) propane, 1,3-bis (tribromosilane) propane, vinyltrimethoxysilane, vinyltriethoxysilane, β- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryl Oxypropylmethyldimethoxysilane, p-styryltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltriethoxysilane, γ -Acryloxypropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β- Aminoethyl) -γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane , N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, dimethoxy-3-mercaptopropyl Methylsilane, 2- (2-aminoethylthioethyl) diethoxymethylsilane, 3- (2-acetoxyethylthiopropyl) dimethoxymethylsilane, 2- (2-aminoethylthioethyl) triethoxysilane, dimeth Methoxymethyl-3- (3-phenoxypropylthiopropyl) silane, bis (triethoxysilylpropyl) disulfide, bis (triethoxysilylpropyl) tetrasulfide, 1,4-bis (triethoxysilyl) Benzene, bis (triethoxysilyl) ethane, 1,6-bis (trimethoxysilyl) hexane, 1,8-bis (triethoxysilyl) octane, 1,2-bis (trimethoxysilyl) decane, Bis (triethoxysilylpropyl) amine, bis (trimethoxysilylpropyl) urea, γ-chloropropyltrimethoxysilane, γ-triethoxysilylpropylmethacrylate, γ- In-laid propyltriethoxysilane and the like can be mentioned silane, trimethyl silanol, diphenyl silane diol, triphenyl silanol.

In addition, although the compound shown below is mentioned as a preferable thing, this invention is not limited to these compounds.

In said each formula, R and R <^1> represent the partial structure chosen from the following structures, respectively. When a plurality of R and R ¹ are present in the molecule, they may be the same as or different from each other, and the synthetic aptitude is preferably the same.

Although component X can also be obtained by synthesis | combining suitably, it is preferable from a cost point to use a commercially available thing. As the component X, for example, commercial products, such as a silane product marketed from Shin-Etsu Chemical Co., Ltd., Toray Dow Corning Co., Ltd., Momentive Performance Materials Co., Ltd., Chiso Co., Ltd., a silane coupling agent, etc. Since this corresponds to this, you may select and use these commercial items suitably for the resin composition of this invention according to the objective.

As the component X in the present invention, a partially hydrolyzed condensate obtained by using one kind of a compound having a hydrolyzable silyl group and / or silanol group or a partially cohydrolyzed condensate obtained by using two or more kinds can be used. Hereinafter, these compounds may be called "partial (co) hydrolysis condensate."

It is preferable that it is a silane compound which has a substituent chosen from a methyl group and a phenyl group as a substituent on a silicon from a versatility, a cost, and the compatibility of a film among the silane compounds as a partial (co) hydrolysis-condensation precursor, specifically methyltrimethoxy Silane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane and diphenyldiethoxysilane are exemplified as preferred precursors.

In this case, as the partial (co) hydrolysis condensate, a dimer of a silane compound as described above (with 1 mole of water acted on 2 moles of silane compound and 2 moles of alcohol desorbed to disiloxane units) to 100 mers, preferably Preferably it is a 2-50 monomer, More preferably, it can use preferably 2-30 monomer, It is also possible to use the partial cohydrolysis condensate which uses two or more types of silane compounds as a raw material.

In addition, such a partial (co) hydrolysis condensate may use what is marketed as a silicon alkoxy oligomer (for example, it is marketed from Shin-Etsu Chemical Co., Ltd.), and also it is hydrolyzable based on a conventional method. You may use what was manufactured by making less than equivalent hydrolyzate react with a silane compound, and then removing by-products, such as alcohol and hydrochloric acid. In manufacturing, when using the alkoxysilanes and acyloxysilanes mentioned above as a hydrolysable silane compound of a raw material used as a precursor, alkali metals, such as hydrochloric acid and a sulfuric acid, alkali metals, such as sodium hydroxide and potassium hydroxide, or alkaline-earth, etc. Alkaline organic substances such as metal hydroxides, triethylamine and the like may be partially hydrolyzed and condensed as reaction catalysts, and when produced directly from chlorosilanes, water and alcohol may be reacted with byproduct hydrochloric acid as a catalyst.

Bis (trialkoxy silyl) alkanes are more preferable, and bis- (3-trimethoxysilyl is more preferable from a viewpoint of the curability, the adhesiveness, the heat-coloring stability, the balance of transparency, and adhesive strength more excellent, and the excellent heat-resistant adhesiveness. Propyl) amine, 1,2-bis (triethoxysilyl) ethane, 1,6-bis (trimethoxysilyl) hexane, 1,7-bis (trimethoxysilyl) heptane, 1,8-bis (tri At least one selected from the group consisting of methoxysilyl) octane, 1,9-bis (trimethoxysilyl) nonane and 1,10-bis (trimethoxysilyl) decane is more preferable, and 1,6-bis ( More preferred are trimethoxysilyl) hexane and bis- (3-trimethoxysilylpropyl) amine.

As for the X component used by this invention, the silicon compound especially represented by Formula (X2) is preferable.

(Wherein X represents a group represented by the formula (X1), and a represents an integer of 2 or more. Ro represents a linking group having a value)

X in Formula (X2) is synonymous with group represented by the said Formula (X1), and its preferable range is also synonymous.

In formula (X2), 2-4 are preferable and, as for a, 2 or 3 is more preferable.

The compound represented by formula (X2) is more preferably a compound represented by the following formula (X3).

(Wherein X represents the formula (X1) and a represents an integer of 2 or more. N represents an integer of 1 to 5. Roo represents a single bond or a linking group of a value.)

X in Formula (X3) is synonymous with group represented by the said Formula (X1), and its preferable range is also synonymous.

In formula (X3), 2-4 are preferable, as for a, 2 or 3 is more preferable, and 2 is especially preferable.

In formula (X3), Roo is a single bond and -CR _2- (R is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms), -S-, -CO-, -O-, a phenylene group, and

It is preferable that it is group which consists of two or more combination of these.

In formula (X3), Roo more preferably consists of a single bond and -CR _2- (R is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms), -S-, -CO-, -O-, and a combination thereof. It is a group consisting of, -S-, and combinations thereof - group, and more preferably a single bond and -CH _2.

In Formula (X3), the integer of 1-3 is preferable, and, as for n, 1 or 2 is more preferable.

100-1500 are preferable and, as for the molecular weight of the silicon compound used by this invention, 250-1100 are more preferable.

Especially in this invention, the silicon compound of Formula (S-1)-Formula (S-17) is employ | adopted preferably.

The component X can be used individually or in combination of 2 types or more, respectively.

In the present invention, the amount of component X is preferably 0.1% by weight or more, and 0.5% by weight or more, based on the total balance of the components excluding the solvent of the resin composition from the viewpoint of the curability, adhesiveness, heat-coloring stability, and the balance between transparency and adhesive strength. More preferred. Although it does not specifically determine about an upper limit, Preferably it is 10 weight% or less, More preferably, it is 5 weight% or less.

(Component C) Photoacid Generator

The photosensitive resin composition of this invention contains the (component C) photo-acid generator.

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

As the component C, a photoacid generator for generating an acid having a pKa of 4 or less is preferable, and a photoacid generator for generating an acid having a pKa of 3 or less is more preferable.

Examples of the photoacid generator include trichloromethyl-s-triazines, sulfonium salts and iodonium salts, quaternary ammonium salts, diazomethane compounds, imidosulfonate compounds and oxime sulfonate compounds. Among them, it is preferable to use an oxime sulfonate compound from the viewpoint of high sensitivity. These photo-acid generators can be used individually by 1 type or in combination of 2 or more types. As these specific examples, Paragraph 0029 of Unexamined-Japanese-Patent No. 2004-264623-the photo-acid generator of paragraph 0032 can be mentioned, 4,7-di-n-butoxy-1- naphthyl tetrahydrothiophenium trifluoro Romethane sulfonate etc. are used preferably.

It is preferable that the photosensitive resin composition of this invention contains the oxime sulfonate compound which has at least 1 of the oxime sulfonate residue represented by following formula (c0) as a (component C) photoacid generator. In addition, the broken line indicates a bonding position with another chemical structure.

It is preferable that the oxime sulfonate compound which has at least 1 of the oxime sulfonate residue represented by said formula (c0) is a compound represented by following formula (c1).

(In formula (c1), R ⁵ and R ⁶ each independently represent a monovalent organic group, R ⁵ and R ⁶ may be linked to each other to form a ring, and R ⁷ represents an alkyl group or an aryl group.)

In formula (c1), R <^5> is a C1-C6 alkyl group, a C1-C4 halogenated alkyl group, a phenyl group, a biphenyl group, a naphthyl group, 2-furyl group, 2-thienyl group, C1-C6 Four alkoxy groups or cyano groups are shown. When R ⁵ is a phenyl group, a biphenyl group, a naphthyl group or an anthranyl group, these groups are substituted with a substituent selected from the group consisting of a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms and a nitro group May be substituted.

R ⁶ in formula (c1) is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, and W The phenyl group which may be substituted, the naphthyl group which may be substituted by W, or the anthranyl group, dialkylamino group, morpholino group, or cyano group which may be substituted by W is shown. R ⁶ and R ⁵ may be bonded to each other to form a 5- or 6-membered ring, and the 5- or 6-membered ring may be bonded to a benzene ring which may have one or two arbitrary substituents.

R ⁷ in formula (c1) is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, and W The phenyl group which may be substituted, the naphthyl group which may be substituted by W, or the anthranyl group which may be substituted by W is shown. The alkyl group may be a cyclic alkyl group. W is a halogen atom, cyano group, nitro group, alkyl group having 1 to 10 carbon atoms, alkoxy group having 1 to 10 carbon atoms, halogenated alkyl group having 1 to 5 carbon atoms or halogenated alkoxy group having 1 to 5 carbon atoms Indicates.

The alkyl group having 1 to 6 carbon atoms represented by R ⁵ may be a straight or branched alkyl group, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group , n-pentyl group, isoamyl group, n-hexyl group or 2-ethylbutyl group.

Examples of the halogenated alkyl group having 1 to 4 carbon atoms represented by R ⁵ include a chloromethyl group, trichloromethyl group, trifluoromethyl group or 2-bromopropyl group.

A methoxy group or an ethoxy group is mentioned as a C1-C4 alkoxy group represented by R <^5> .

When R ⁵ represents a phenyl group, a biphenyl group, a naphthyl group or an anthranyl group, these groups are halogen atoms (e.g., chlorine atom, bromine atom, iodine atom, etc.), hydroxyl groups, alkyl groups having 1 to 4 carbon atoms (e.g. For example, a methyl group, an ethyl group, a propyl group, isopropyl group, n-butyl group, sec-butyl group, tert- butyl group), the C1-C4 alkoxy group (for example, a methoxy group, an ethoxy group, n -May be substituted by a substituent selected from the group consisting of propoxy group, i-propoxy group, n-butoxy group) and nitro group.

Specific examples of the alkyl group having 1 to 10 carbon atoms represented by R ⁶ include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, n-amyl group, i-amyl group, s-amyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, etc. are mentioned.

Specific examples of the alkoxy group having 1 to 10 carbon atoms represented by R ⁶ include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, n-amyloxy group, n-octyl octa A time period, n-decyloxy group, etc. are mentioned.

Specific examples of the halogenated alkyl group having 1 to 5 carbon atoms represented by R ⁶ include trifluoromethyl group, pentafluoroethyl group, perfluoro-n-propyl group, perfluoro-n-butyl group, and perfluoro-n -Amyl and the like.

Specific examples of the halogenated alkoxy group having 1 to 5 carbon atoms represented by R ⁶ include a trifluoromethoxy group, a pentafluoroethoxy group, a perfluoro-n-propoxy group, a perfluoro-n-butoxy group, Perfluoro-n-amyloxy group etc. are mentioned.

Specific examples of the phenyl group which may be substituted with W represented by R ⁶ include o-tril group, m-tril group, p-tril group, o-ethylphenyl group, m-ethylphenyl group, p-ethylphenyl group, p- (n- Propyl) phenyl group, p- (i-propyl) phenyl group, p- (n-butyl) phenyl group, p- (i-butyl) phenyl group, p- (s-butyl) phenyl group, p- (t-butyl) phenyl group, p -(n-amyl) phenyl group, p- (i-amyl) phenyl group, p- (t-amyl) phenyl group, o-methoxyphenyl group, m-methoxyphenyl group, p-methoxyphenyl group, o-ethoxyphenyl group, m-ethoxyphenyl group, p-ethoxyphenyl group, p- (n-propoxy) phenyl group, p- (i-propoxy) phenyl group, p- (n-butoxy) phenyl group, p- (i-butoxy) Phenyl group, p- (s-butoxy) phenyl group, p- (t-butoxy) phenyl group, p- (n-amyloxy) phenyl group, p- (i-amyloxy) phenyl group, p- (t-amyloxy) Phenyl group, p-chlorophenyl group, p-bromophenyl group, p-fluorophenyl group, 2,4-dichlorophenyl group, 2,4-dibromophenyl group, 2,4-difluorophenyl group, 2,4,6- Dichlorophenyl group, 2,4,6-tribromophenyl group, 2,4,6-trifluorophenyl group, pentachlorophenyl group, pentabromophenyl group, pentafluorophenyl group, p-biphenylyl group, etc. are mentioned.

As a specific example of the naphthyl group which may be substituted by W represented by R <^6> , 2-methyl-1- naphthyl group, 3-methyl-1- naphthyl group, 4-methyl-1- naphthyl group, 5-methyl-1- naphth Tyl group, 6-methyl-1-naphthyl group, 7-methyl-1-naphthyl group, 8-methyl-1-naphthyl group, 1-methyl-2-naphthyl group, 3-methyl-2-naphthyl group, 4-methyl -2-naphthyl group, 5-methyl-2-naphthyl group, 6-methyl-2-naphthyl group, 7-methyl-2-naphthyl group, 8-methyl-2-naphthyl group, etc. are mentioned.

As a specific example of the anthranyl group which may be substituted by W represented by R <^6> , 2-methyl-1- anthranyl group, 3-methyl-1- anthranyl group, 4-methyl-1- anthranyl group, 5-methyl-1- anthra Neyl group, 6-methyl-1-antranyl group, 7-methyl-1-antranyl group, 8-methyl-1-antranyl group, 9-methyl-1-antranyl group, 10-methyl-1-antranyl group, 1-methyl -2-anthranyl group, 3-methyl-2-antranyl group, 4-methyl-2-antranyl group, 5-methyl-2-antranyl group, 6-methyl-2-antranyl group, 7-methyl-2-antranyl group , 8-methyl-2-anthranyl group, 9-methyl-2-anthranyl group, 10-methyl-2-anthranyl group, and the like.

Examples of the dialkylamino group represented by R ⁶ include a dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, diphenylamino group and the like.

Specific examples of the alkyl group having 1 to 10 carbon atoms represented by R ⁷ include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, n-amyl group, i-amyl group, s-amyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, etc. are mentioned.

As a specific example of the C1-C10 alkoxy group represented by R <^7> , a methoxy group, an ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, n-amyloxy group, n-octyl octa A time period, n-decyloxy group, etc. are mentioned.

Specific examples of the halogenated alkyl group having 1 to 5 carbon atoms represented by R ⁷ include trifluoromethyl group, pentafluoroethyl group, perfluoro-n-propyl group, perfluoro-n-butyl group, and perfluoro-n -Amyl and the like.

Specific examples of the halogenated alkoxy group having 1 to 5 carbon atoms represented by R ⁷ include trifluoromethoxy group, pentafluoroethoxy group, perfluoro-n-propoxy group, perfluoro-n-butoxy group, Perfluoro-n-amyloxy group etc. are mentioned.

Specific examples of the phenyl group which may be substituted with W represented by R ⁷ include o-tril group, m-tril group, p-tril group, o-ethylphenyl group, m-ethylphenyl group, p-ethylphenyl group, p- (n- Propyl) phenyl group, p- (i-propyl) phenyl group, p- (n-butyl) phenyl group, p- (i-butyl) phenyl group, p- (s-butyl) phenyl group, p- (t-butyl) phenyl group, p -(n-amyl) phenyl group, p- (i-amyl) phenyl group, p- (t-amyl) phenyl group, o-methoxyphenyl group, m-methoxyphenyl group, p-methoxyphenyl group, o-ethoxyphenyl group, m-ethoxyphenyl group, p-ethoxyphenyl group, p- (n-propoxy) phenyl group, p- (i-propoxy) phenyl group, p- (n-butoxy) phenyl group, p- (i-butoxy) Phenyl group, p- (s-butoxy) phenyl group, p- (t-butoxy) phenyl group, p- (n-amyloxy) phenyl group, p- (i-amyloxy) phenyl group, p- (t-amyloxy) Phenyl group, p-chlorophenyl group, p-bromophenyl group, p-fluorophenyl group, 2,4-dichlorophenyl group, 2,4-dibromophenyl group, 2,4-difluorophenyl group, 2,4,6- Dichlorophenyl group, 2,4,6-tribromophenyl group, 2, 4,6-trifluorophenyl group, pentachlorophenyl group, pentabromophenyl group, pentafluorophenyl group, p-biphenylyl group, etc. are mentioned.

As a specific example of the naphthyl group which may be substituted by W represented by R <^7> , 2-methyl-1- naphthyl group, 3-methyl-1- naphthyl group, 4-methyl-1- naphthyl group, 5-methyl-1- naphth Tyl group, 6-methyl-1-naphthyl group, 7-methyl-1-naphthyl group, 8-methyl-1-naphthyl group, 1-methyl-2-naphthyl group, 3-methyl-2-naphthyl group, 4-methyl -2-naphthyl group, 5-methyl-2-naphthyl group, 6-methyl-2-naphthyl group, 7-methyl-2-naphthyl group, 8-methyl-2-naphthyl group, etc. are mentioned.

As an example of the anthranyl group which may be substituted by W represented by R <^7> , 2-methyl-1- anthranyl group, 3-methyl-1- anthranyl group, 4-methyl-1- anthranyl group, 5-methyl-1- anthra Neyl group, 6-methyl-1-antranyl group, 7-methyl-1-antranyl group, 8-methyl-1-antranyl group, 9-methyl-1-antranyl group, 10-methyl-1-antranyl group, 1-methyl -2-anthranyl group, 3-methyl-2-antranyl group, 4-methyl-2-antranyl group, 5-methyl-2-antranyl group, 6-methyl-2-antranyl group, 7-methyl-2-antranyl group , 8-methyl-2-anthranyl group, 9-methyl-2-anthranyl group, 10-methyl-2-anthranyl group, and the like.

Specific examples of the alkyl group having 1 to 10 carbon atoms represented by W, the alkoxy group having 1 to 10 carbon atoms, the halogenated alkyl group having 1 to 5 carbon atoms, and the alkoxy halide having 1 to 5 carbon atoms are R ⁶ or R ^7. The same as those listed as specific examples of the alkyl group having 1 to 10 carbon atoms, the alkoxy group having 1 to 10 carbon atoms, the halogenated alkyl group having 1 to 5 carbon atoms, and the halogenated alkoxy group having 1 to 5 carbon atoms It can be mentioned.

R ⁶ and R ⁵ may be bonded to each other to form a five-membered ring or a six-membered ring.

When R ⁶ and R ⁵ are bonded to each other to form a 5- or 6-membered ring, examples of the 5- or 6-membered ring include carbocyclic groups and heterocyclic rings. For example, cyclopentane, cyclohexane, cycloheptane, pyrrole Or furan, thiophene, imidazole, oxazole, thiazole, pyran, pyridine, pyrazine, morpholine, piperidine or piperazine ring. The 5-membered or 6-membered ring may be bonded to a benzene ring which may have an arbitrary substituent. Examples thereof include tetrahydronaphthalene, dihydroanthracene, indene, chroman, fluorene, xanthene or thioxanthene ring system . The 5- or 6-membered ring may contain a carbonyl group, and examples thereof include cyclohexadienone, naphthalenone, and anthrone ring systems.

One of the preferred embodiments of the compound represented by the formula (c1) is a compound represented by the following formula (c1-1). The compound represented by formula (c1-1) is a compound in which R ⁶ and R ⁵ in formula (c1) are bonded to form a five-membered ring.

(Formula (c1-1) of R ⁷ is R ⁷ and the consent of the formula (c1), X is an alkyl group, an alkoxy group or a halogen atom, t represents an integer of 0 ~ 3, t is 2 or When 3, several X may be same or different)

As an alkyl group represented by X, a C1-C4 linear or branched alkyl group is preferable.

As an alkoxy group represented by X, a C1-C4 linear or branched alkoxy group is preferable.

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

As t, 0 or 1 is preferable.

In formula (c1-1), t is 1, X is a methyl group, the substitution position of X is an ortho position, R <^7> is a linear alkyl group of 1-10 carbon atoms, and 7,7- dimethyl- 2-iodine Particularly preferred are compounds which are nobornylmethyl groups or p-tolyl groups.

Specific examples of the oxime sulfonate compound represented by formula (c1-1) include the following compound (i), compound (ii), compound (VII), compound (VII), and the like. May be used, and two or more types may be used in combination. Compound (i)-(v) can be obtained as a commercial item.

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

As one of the preferable embodiment of a compound represented by a formula (c1),

R ⁵ represents an alkyl group having 1 to 4 carbon atoms, a trifluoromethyl group, a phenyl group, a chlorophenyl group, a dichlorophenyl group, a methoxyphenyl group, a 4-biphenyl group, a naphthyl group or an anthranyl group;

R ⁶ represents a cyano group;

R ⁷ is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, or a phenyl group which may be substituted with W , Naphthyl group which may be substituted by W or an anthranyl group which may be substituted by W, W represents a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms And a halogenated alkyl group having 1 to 5 carbon atoms or a halogenated alkoxy group having 1 to 5 carbon atoms.

It is also preferable that it is a compound represented by a following formula (c1-2) as a compound represented by a formula (c1).

R <^8> shows a halogen atom, a hydroxyl group, a C1-C4 alkyl group, a C1-C4 alkoxy group, or a nitro group in a formula (c1-2), and L shows the integer of 0-5. R ⁷ is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, or a phenyl group which may be substituted with W , Naphthyl group which may be substituted by W or an anthranyl group which may be substituted by W, W represents a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms And a halogenated alkyl group having 1 to 5 carbon atoms or a halogenated alkoxy group having 1 to 5 carbon atoms.

As R <^7> in Formula (c1-2), a methyl group, an ethyl group, n-propyl group, n-butyl group, n-octyl group, trifluoromethyl group, pentafluoroethyl group, perfluoro-n-propyl group, Perfluoro-n-butyl group, p-tril group, 4-chlorophenyl group, or pentafluorophenyl group is preferable, and it is especially preferable that they are a methyl group, an ethyl group, n-propyl group, n-butyl group, or p-tril group.

As a halogen atom represented by R <^8> , a fluorine atom, a chlorine atom, or a bromine atom is preferable.

As the alkyl group having 1 to 4 carbon atoms represented by R ⁸ , a methyl group or an ethyl group is preferable.

As the alkoxy group having 1 to 4 carbon atoms represented by R ⁸ , a methoxy group or an ethoxy group is preferable.

As L, 0-2 are preferable and 0-1 are especially preferable.

As a preferable embodiment of the compound contained in the compound represented by Formula (c1-2) among the compound represented by Formula (c1), R <^5> shows a phenyl group or 4-methoxyphenyl group in Formula (c1), and R <^6> is cyan. It represents embodiment, and R <^7> is embodiment which shows a methyl group, an ethyl group, n-propyl group, n-butyl group, or 4-tril group.

Although the preferable example of the compound contained in the compound represented by a formula (c1-2) among the compound represented by a formula (c1) below is shown, this invention is not limited to these.

α- (methylsulfonyloxyimino) benzylcyanide (R ⁵ = phenyl group, R ⁶ = cyano group, R ⁷ = methyl group)

α- (ethylsulfonyloxyimino) benzylcyanide (R ⁵ = phenyl group, R ⁶ = cyano group, R ⁷ = ethyl group)

α- (n-propylsulfonyloxyimino) benzyl cyanide (R ⁵ = phenyl group, R ⁶ = cyano group, R ⁷ = n-propyl group)

α- (n-butylsulfonyloxyimino) benzyl cyanide (R ⁵ = phenyl group, R ⁶ = cyano group, R ⁷ = n-butyl group)

α- (4-toluenesulfonyloxyimino) benzyl cyanide (R ⁵ = phenyl group, R ⁶ = cyano group, R ⁷ = 4-tril group)

α-[(methylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile (R ⁵ = 4-methoxyphenyl group, R ⁶ = cyano group, R ⁷ = methyl group)

α-[(ethylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile (R ⁵ = 4-methoxyphenyl group, R ⁶ = cyano group, R ⁷ = ethyl group)

α-[(n-propylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile (R ⁵ = 4-methoxyphenyl group, R ⁶ = cyano group, R ⁷ = n-propyl group)

α-[(n-butylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile (R ⁵ = 4-methoxyphenyl group, R ⁶ = cyano group, R ⁷ = n-butyl group)

α-[(4-toluenesulfonyloxyimino) -4-methoxyphenyl] acetonitrile (R ⁵ = 4-methoxyphenyl group, R ⁶ = cyano group, R ⁷ = 4-trilyl group)

Moreover, as a compound which has at least one oxime sulfonate residue represented by said formula (c0), the oxime sulfonate represented by a following formula (OS-3), a formula (OS-4), or a formula (OS-5) It is preferable that it is a compound.

(In formula (OS-3)-(OS-5), R <^1> represents an alkyl group, an aryl group, or heteroaryl group, and two or more R <^2> represents a hydrogen atom, an alkyl group, an aryl group, or a halogen atom each independently, R ⁶ present each independently represents a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group, X represents O or S, n represents 1 or 2, and m represents 0 to Represents an integer of 6)

The alkyl group, aryl group, or heteroaryl group represented by R ¹ in the formulas (OS-3) to (OS-5) may have a substituent.

It is preferable that it is a C1-C30 alkyl group which may have a substituent as an alkyl group represented by R <^1> in said Formula (OS-3)-(OS-5).

Moreover, as an aryl group represented by R <^1> in said Formula (OS-3)-(OS-5), the C6-C30 aryl group which may have a substituent is preferable.

Moreover, as a heteroaryl group represented by R <^1> in said Formula (OS-3)-(OS-5), the heteroaryl group of 4-30 total carbons which may have a substituent is preferable, and it should just be at least 1 heteroaromatic ring. For example, the heteroaromatic ring and the benzene ring may be condensed.

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

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

It is preferable that one or two of R <^2> which exists in the compound in said Formula (OS-3)-(OS-5) two or more are an alkyl group, an aryl group, or a halogen atom, and one is an alkyl group, an aryl group, or a halogen atom It is more preferable, it is especially preferable that one is an alkyl group and the remainder is a hydrogen atom.

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

As a substituent which the alkyl group or aryl group represented by R <^2> may have, the group similar to the substituent which the alkyl group or aryl group in said R <^1> may have can be illustrated.

As said alkyl group represented by R <^2> in said Formula (OS-3)-(OS-5), it is preferable that it is a C1-C12 alkyl group which may have a substituent, and the C1-C6 alkyl group which may have a substituent is preferable. It is more preferable that is.

As an alkyl group represented by R <^2> , a methyl group, an ethyl group, n-propyl group, n-butyl group, n-hexyl group is preferable, and a methyl group is more preferable.

As an aryl group represented by R <^2> in said Formula (OS-3)-(OS-5), it is preferable that it is a C6-C30 aryl group which may have a substituent.

As an aryl group represented by R <^2> , a phenyl group, p-methylphenyl group, o-chlorophenyl group, p-chlorophenyl group, o-methoxyphenyl group, and p-phenoxyphenyl group are preferable.

In said formula (OS-3)-(OS-5), X represents O or S, and it is preferable that it is O.

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

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

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

It is preferable that it is a C1-C30 alkyl group which may have a substituent as said alkyl group represented by R <^6> in said Formula (OS-3)-(OS-5).

As the alkyloxy group represented by R ⁶ , a methyloxy group, ethyloxy group, butyloxy group, hexyloxy group, phenoxyethyloxy group, trichloromethyloxy group or ethoxyethyloxy group is preferable.

Examples of the aminosulfonyl group for R ⁶ include a methylaminosulfonyl group, dimethylaminosulfonyl group, phenylaminosulfonyl group, methylphenylaminosulfonyl group, and aminosulfonyl group.

Examples of the alkoxysulfonyl group represented by R ⁶ include a methoxysulfonyl group, an ethoxysulfonyl group, a propyloxysulfonyl group, and a butyloxysulfonyl group.

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

Moreover, in said formula (OS-3)-(OS-5), m represents the integer of 0-6, it is preferable that it is an integer of 0-2, It is more preferable that it is 0 or 1, It is especially preferable that it is 0 .

Moreover, it is especially preferable that the compound represented by said formula (OS-3) is a compound represented by a following formula (OS-6), a formula (OS-10), or a formula (OS-11), The said formula (OS- It is particularly preferable that the compound represented by 4) is a compound represented by the following formula (OS-7), and the compound represented by the formula (OS-5) is represented by the following formula (OS-8) or formula (OS-9). It is especially preferable that it is a compound represented by.

R <^1> represents an alkyl group, an aryl group, or a heteroaryl group in a formula (OS-6)-(OS-11), R <^7> represents a hydrogen atom or a bromine atom, R <^8> is a hydrogen atom, a C1-C8 alkyl group, A halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or a chlorophenyl group, R ⁹ represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and R ¹⁰ represents a hydrogen atom or a methyl group .

The expression (OS-6) ~ R ¹ in (OS-11) is R ¹ and agreed in the formula (OS-3) ~ (OS -5), a preferred embodiment versa.

R <^7> in said Formula (OS-6) represents a hydrogen atom or a bromine atom, and it is preferable that it is a hydrogen atom.

R <^8> in said Formula (OS-6)-(OS-11) is a hydrogen atom, a C1-C8 alkyl group, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group, or chloro It is preferable that it is a C1-C8 alkyl group, a halogen atom, or a phenyl group, It is more preferable that it is a C1-C8 alkyl group, It is still more preferable that it is a C1-C6 alkyl group, It is especially preferable that it is a methyl group .

R <^9> in the said Formula (OS-8) and formula (OS-9) represents a hydrogen atom, a halogen atom, a methyl group, or a methoxy group, and it is preferable that it is a hydrogen atom.

R <^10> in said Formula (OS-8)-(OS-11) represents a hydrogen atom or a methyl group, and it is preferable that it is a hydrogen atom.

In addition, in the said oxime sulfonate compound, either one or a mixture may be sufficient about the stereo structure (E, Z) of an oxime.

Although the following exemplary compound is mentioned as a specific example of the oxime sulfonate compound represented by said Formula (OS-3)-(OS-5), This invention is not limited to these.

As another preferable embodiment of the oxime sulfonate compound which has at least one oxime sulfonate residue represented by said formula (c0), Paragraph 0117 of Unexamined-Japanese-Patent No. 2011-209719-0129 can also be mentioned. .

It is preferable that the photosensitive resin composition of this invention does not contain a 1, 2- quinonediazide compound as a (component C) photo-acid generator sensitive to actinic light. The reason is that the 1,2-quinonediazide compound generates a carboxyl group by a sequential photochemical reaction, but its quantum yield is 1 or less, and its sensitivity is lower than that of the oxime sulfonate compound.

On the other hand, since the oxime sulfonate compound acts as a catalyst for the deprotection of the protected acid group, the acid produced in response to actinic light contributes to a large number of deprotection reactions by the action of one photon. The yield exceeds 1 and, for example, a large value such as a power of 10 is assumed to be obtained as a result of so-called chemical amplification.

It is preferable that it is 0.1-10 weight part with respect to 100 weight part of upper content of component A and component B, and, as for content of the (component C) photoacid generator in the photosensitive resin composition of this invention, it is more preferable that it is 0.5-10 weight part. .

(Component D) Solvent

It is preferable that the photosensitive resin composition of this invention contains the (component D) solvent. It is preferable that the photosensitive resin composition of this invention is prepared as a solution which melt | dissolved each component of this invention in the (component D) solvent.

As a solvent used for the photosensitive resin composition of this invention, a well-known solvent can be used and ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol Dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol mono Alkyl ether acetates, esters, ketones, amides, lactones, etc. can be illustrated. As a solvent used for the photosensitive resin composition of this invention, the solvent of Paragraph 0074 of Unexamined-Japanese-Patent No. 2009-258722 is mentioned, for example.

Diethylene glycol ethyl methyl ether and / or propylene glycol monomethyl ether acetate are particularly preferable in the above-mentioned solvents.

These solvents can be used individually by 1 type or in mixture of 2 or more types. It is preferable to use together 1 type individually or 2 types of solvents which can be used for this invention, It is more preferable to use 2 types together, It is more preferable to use together propylene glycol monoalkyl ether acetates and diethylene glycol dialkyl ethers. More preferred.

It is preferable that content of the component D in the photosensitive resin composition of this invention is 50-3,000 weight part with respect to 100 weight part of components A, It is more preferable that it is 100-2,000 weight part, It is further more preferable that it is 150-1,500 weight part.

It is preferable that content of the (component D) solvent in the photosensitive resin composition of this invention is 50-3,000 weight part per 100 weight part of total content of component A and component B, It is more preferable that it is 100-2,000 weight part, 150-1,500 It is more preferable that it is a weight part.

<Other Ingredients>

The photosensitive resin composition of this invention can contain another component.

As other components, the photosensitive resin composition of the present invention preferably contains a photosensitizer from the viewpoint of sensitivity, preferably contains a basic compound from the viewpoint of liquid storage stability, and preferably contains a crosslinking agent from the viewpoint of membrane properties. And it is preferable to contain an adhesive improving agent from a viewpoint of board | substrate adhesiveness, and it is preferable to contain surfactant from a viewpoint of applicability | paintability.

Hereinafter, the other component which can be contained in the photosensitive resin composition of this invention is demonstrated.

[Photosensitizer]

It is preferable that the photosensitive resin composition of this invention contains a photosensitizer.

By containing a photosensitizer, it is effective for the improvement of exposure sensitivity, and it is especially effective when an exposure light source is g and h-ray mixed lines.

As the photosensitizer, anthracene derivatives, acridon derivatives, thioxanthone derivatives, coumarin derivatives, basestyryl derivatives and distyrylbenzene derivatives are preferable.

Anthracene derivatives include anthracene, 9,10-dibutoxyanthracene, 9,10-dichloroanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9-hydroxymethylanthracene, 9-bromoanthracene, 9-chloroanthracene, 9,10-dibromoanthracene, 2-ethylanthracene and 9,10-dimethoxyanthracene are preferred.

As the acridon derivative, acridon, N-butyl-2-chloroacridone, N-methylacridone, 2-methoxyacridone, and N-ethyl-2-methoxyacridone are preferable.

As a thioxanthone derivative, thioxanthone, diethyl thioxanthone, 1-chloro-4- propoxy thioxanthone, and 2-chloro thioxanthone are preferable.

As coumarin derivatives, coumarin-1, coumarin-6H, coumarin-110, and coumarin-102 are preferable.

Examples of the base styryl derivatives include 2- (4-dimethylaminostyryl) benzoxazole, 2- (4-dimethylaminostyryl) benzothiazole and 2- (4-dimethylaminostyryl) naphthothiazole. .

Examples of the distyrylbenzene derivatives include distyrylbenzene, di (4-methoxystyryl) benzene, and di (3,4,5-trimethoxystyryl) benzene.

Among these, an anthracene derivative is preferable and 9,10- dialkoxy anthracene (C1-C6 of an alkoxy group) is more preferable.

The following is mentioned as a specific example of a photosensitizer. In the following, Me represents a methyl group, Et represents an ethyl group, and Bu represents a butyl group.

It is preferable that it is 0.1-10 weight part with respect to 100 weight part of total content of component A and the component B, and, as for content of the photosensitizer in the photosensitive resin composition of this invention, it is more preferable that it is 0.5-10 weight part. If content of a photosensitizer is 0.1 weight part or more, desired sensitivity will be easy to be obtained, and if it is 10 weight part or less, transparency of a coating film will be easy to be ensured.

[Basic compound]

It is preferable that the photosensitive resin composition of this invention contains a basic compound from a viewpoint of liquid storage stability.

It can be used selecting arbitrarily as a basic compound from what is used by chemically amplified resist. For example, aliphatic amine, aromatic amine, heterocyclic amine, quaternary ammonium hydroxide, quaternary ammonium salt of carboxylic acid, etc. are mentioned.

Examples of the aliphatic amines include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine and triethanol. Amine, dicyclohexylamine, dicyclohexylmethylamine, and the like.

As aromatic amine, aniline, benzylamine, N, N- dimethylaniline, diphenylamine, etc. are mentioned, for example.

Examples of heterocyclic amines include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4- Dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinic acid amide, quinoline, 8-oxyquinoline , Pyrazine, pyrazole, pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, N-cyclohexyl-N '-[2- (4-morpholinyl) ethyl ] Thiourea, 1, 5- diazabicyclo [4.3.0] -5-nonene, 1,8- diazabicyclo [5.3.0] -7-undecene, etc. are mentioned.

As quaternary ammonium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, tetra-n-hexyl ammonium hydroxide, etc. are mentioned, for example.

As quaternary ammonium salt of carboxylic acid, tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, tetra-n-butylammonium benzoate, etc. are mentioned, for example.

Although the basic compound which can be used for this invention may be used individually by 1 type, or may use 2 or more types together, It is preferable to use 2 or more types together, It is more preferable to use 2 types together, It is more preferable to use 2 types of heterocyclic amines together More preferred.

It is preferable that it is 0.001-1 weight part with respect to 100 weight part of total content of component A and the component B, and, as for content of the basic compound in the photosensitive resin composition of this invention, it is more preferable that it is 0.002-0.2 weight part.

[Crosslinking agent]

It is preferable that the photosensitive resin composition of this invention contains a crosslinking agent as needed. By adding a crosslinking agent, the cured film obtained by the photosensitive resin composition of this invention can be made a stronger film.

As a crosslinking agent, the compound which has two or more epoxy groups or oxetanyl group, the alkoxy methyl group containing crosslinking agent, or the compound which has at least 1 ethylenically unsaturated double bond can be added, for example in the molecule | numerator demonstrated below.

Among these crosslinking agents, a compound having two or more epoxy groups or oxetanyl groups in the molecule is preferable, and an epoxy resin is particularly preferable.

It is preferable that it is 0.05-50 weight part with respect to the total solid of the photosensitive resin composition, As for the addition amount of the crosslinking agent in the photosensitive resin composition of this invention, it is more preferable that it is 0.5-44 weight part, It is still more preferable that it is 3-40 weight part. By adding in this range, the cured film excellent in mechanical strength and solvent resistance is obtained.

Compounds having two or more epoxy groups or oxetanyl groups in the molecule

As a specific example of the compound which has two or more epoxy groups in a molecule | numerator, a bisphenol-A epoxy resin, a bisphenol F-type epoxy resin, a phenol novolak-type epoxy resin, a cresol novolak-type epoxy resin, an aliphatic epoxy resin, etc. are mentioned.

As a specific example of the compound which has two or more epoxy groups in a molecule | numerator, a bisphenol-A epoxy resin, a bisphenol F-type epoxy resin, a phenol novolak-type epoxy resin, a cresol novolak-type epoxy resin, an aliphatic epoxy resin, etc. are mentioned.

These can be obtained as a commercial item, and what was described in Paragraph 0051-Paragraph 0053 of Unexamined-Japanese-Patent No. 2009-258722, such as JER150S65 and JER1031S (all are the Mitsubishi Kagaku Co., Ltd. make). These may be used alone or in combination of two or more.

Among these, an epoxy resin is mentioned preferably, A bisphenol A-type epoxy resin, a bisphenol F-type epoxy resin, and a phenol novolak-type epoxy resin are more preferable, A bisphenol A-type epoxy resin is especially preferable.

As a specific example of the compound which has two or more oxetanyl groups in a molecule | numerator, AaronoxetaneOXT-121, OXT-221, OX-SQ, PNOX (above, Toagosei Co., Ltd. product) can be used.

In addition, it is preferable to use the compound containing an oxetanyl group individually or in mixture with the compound containing an epoxy group.

Among these, 1-50 weight part is preferable when the addition amount to the photosensitive resin composition of this invention of the compound which has two or more epoxy groups or oxetanyl group in a molecule | numerator makes the total content of component A and component B 100 weight part, 30 weight part is more preferable.

An alkoxymethyl group-containing crosslinking agent or a compound having at least one ethylenically unsaturated double bond

As the alkoxymethyl group-containing crosslinking agent, alkoxymethylated melamine, alkoxymethylated benzoguanamine, alkoxymethylated glycoluril, alkoxymethylated urea and the like are preferable. Moreover, as a compound which has at least 1 ethylenically unsaturated double bond, (meth) acrylate compounds, such as monofunctional (meth) acrylate, bifunctional (meth) acrylate, and trifunctional or more (meth) acrylate, can be used preferably. Can be.

Specific examples of the compound having an alkoxymethyl group-containing crosslinking agent or at least one ethylenically unsaturated double bond include those described in paragraphs 0093 to 0100 of Japanese Patent Application Laid-Open No. 2011-170305, and the same also applies to a preferable range of addition amount and combination. .

[Contact improver]

It is preferable that the photosensitive resin composition of this invention contains an adhesion | attachment improving agent from a viewpoint of board | substrate adhesiveness.

The adhesion improving agent which can be used for the photosensitive resin composition of this invention is made of inorganic materials used as a board | substrate, for example, silicon compounds, such as silicon, silicon oxide, silicon nitride, metals, such as molybdenum, titanium, indium tin oxide, gold, copper, aluminum, and the like. It is a compound which improves the adhesiveness of an insulating film. Specifically, a silane coupling agent, a thiol type compound, etc. are mentioned. The silane coupling agent as the adhesion improving agent used in the present invention is intended to modify the interface, and any known one can be used without particular limitation.

Among these, a silane coupling agent can be illustrated preferably. However, the silane coupling agent of this invention refers to the compound which has one hydrolyzable silyl group or silanol group in 1 molecule, and the silicon compound corresponding to component X is not contained in the silane coupling agent of this invention.

As a preferable silane coupling agent, (gamma) -aminopropyl trimethoxysilane, (gamma) -aminopropyl triethoxysilane, (gamma)-glycidoxy propyltrialkoxy silane, (gamma)-glycidoxy propyl alkyl dialkoxysilane, (gamma)-meta Cryloxypropyl trialkoxysilane, (gamma)-methacryloxypropyl alkyl dialkoxysilane, (gamma)-chloropropyl trialkoxysilane, (gamma)-mercaptopropyl trialkoxysilane, (beta)-(3, 4- epoxycyclohexyl) ethyltrialkoxysilane And vinyltrialkoxysilane.

Among these, γ-glycidoxypropyltrialkoxysilane and γ-methacryloxypropyltrialkoxysilane are more preferable, and γ-glycidoxypropyltrialkoxysilane is more preferable.

These may be used alone or in combination of two or more. They are effective for improving the adhesiveness with a board | substrate and also for adjusting the taper angle with a board | substrate.

0.1-20 weight part is preferable with respect to 100 weight part of total content of component A and the component B, and, as for content of the adhesion | attachment improving agent in the photosensitive resin composition of this invention, 0.5-10 weight part is more preferable.

[Surfactants]

It is preferable that the photosensitive resin composition of this invention contains surfactant from a viewpoint of applicability | paintability.

As the surfactant, any of anionic, cationic, nonionic or zwitterionic can be used, but the preferred surfactant is a nonionic surfactant.

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

It is more preferable that the photosensitive resin composition of this invention contains a fluorine type surfactant and / or a silicone type surfactant as surfactant.

As these fluorine type surfactant and silicone type surfactant, For example, Unexamined-Japanese-Patent No. 62-36663, Unexamined-Japanese-Patent No. 61-226746, Unexamined-Japanese-Patent No. 61-226745, Japan-Patent No. 62-170950, Japan Japanese Patent Laid-Open No. 63-34540, Japanese Patent Laid-Open No. 7-230165, Japanese Patent Laid-Open No. 8-62834, Japanese Patent Laid-Open No. 9-54432, Japanese Patent Laid-Open No. 9-5988, Japanese Patent Laid-Open 2001-330953 The surfactant as described in each publication is mentioned, Commercially available surfactant can also be used.

As a commercially available surfactant which can be used, for example, F-top EF301, EF303 (above, Shin Akita Kasei Co., Ltd.), fluoride FC430, 431 (above, Sumitomo Industries Co., Ltd.), Megapack F171, F173 , F176, F189, R08 (above, made by DIC Corporation), Supron S-382, SC101, 102, 103, 104, 105, 106 (above, made by Asahi Glass Co., Ltd.), PolyFox series (made by OMNOVA Corporation) Fluorine-based surfactants such as a) or silicone-based surfactants. Moreover, polysiloxane polymer KP-341 (made by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicone type surfactant.

Moreover, the weight average molecular weight of polystyrene conversion measured by the gel permeation chromatography in the case of containing the structural unit A and structural unit B represented by following formula (1) as a surfactant, and using tetrahydrofuran (THF) as a solvent. The copolymer whose (Mw) is 1,000 or more and 10,000 or less is mentioned as a preferable example.

(In formula (1), R <^1> and R <^3> respectively independently represents a hydrogen atom or a methyl group, R <^2> represents a C1-C4 linear alkylene group, R <^4> represents a hydrogen atom or C1-C4 or less Represents an alkyl group, L represents an alkylene group having 3 to 6 carbon atoms, p and q are weight percentages representing the polymerization ratio, p represents a numerical value of 10% by weight to 80% by weight, and q is 20% by weight or more and 90% by weight or less, r represents an integer of 1 or more and 18 or less, n represents an integer of 1 or more and 10 or less)

It is preferable that said L is a branched alkylene group represented by following formula (2). R <^5> in Formula (2) represents a C1-C4 alkyl group, A C1-C3 alkyl group is preferable at the point of compatibility and the wettability with respect to a to-be-coated surface, and C2 or 3 Alkyl groups are more preferred.

As for the weight average molecular weight (Mw) of the said copolymer, 1,500 or more and 5,000 or less are more preferable.

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

It is preferable that the addition amount of surfactant in the photosensitive resin composition of this invention is 10 weight part or less with respect to 100 weight part of total contents of component A and component B, It is more preferable that it is 0.01-10 weight part, It is 0.01-1 weight part More preferred.

<Others>

To the photosensitive resin composition of this invention, other components, such as a plasticizer, a thermal radical generator, a thermal acid generator, an acid increasing agent, a development promoter, and antioxidant, can be added as needed. About these components, the thing of Unexamined-Japanese-Patent No. 2009-98616, the Unexamined-Japanese-Patent No. 2009-244801, etc. can be used, for example. Moreover, you may add the various ultraviolet absorbers, metal deactivator, etc. which were described in "extension of polymer additives (the daily industrial newspaper)" to the photosensitive resin composition of this invention.

(Formation method of hardened film)

Next, the formation method of the cured film of this invention is demonstrated.

Although the formation method of the cured film of this invention does not have a restriction | limiting in particular except using the positive photosensitive resin composition of this invention, It is preferable to include the process of the following (1)-(5).

(1) Process of apply | coating positive type photosensitive resin composition of this invention on board | substrate

(2) Process of removing solvent from apply | coated photosensitive resin composition

(3) Process of exposing photosensitive resin composition from which solvent was removed by actinic light

(4) Process of developing exposed photosensitive resin composition with aqueous developing solution

(5) Post-baking step of thermosetting the developed photosensitive resin composition

In the formation method of the cured film of this invention, you may perform the image development process of said (4), without performing heat processing after the exposure in the said exposure process.

Moreover, you may further include the process of carrying out the whole surface exposure of the photosensitive resin composition developed before the said post-baking process.

Moreover, it is preferable that the formation method of the cured film of this invention further includes the dry etching process of carrying out dry etching with respect to the board | substrate which has the cured film obtained by (6) thermosetting.

Each step will be described below in order.

In the application | coating process of (1), it is preferable to set it as the wet film which apply | coats the positive photosensitive resin composition of this invention on a board | substrate and contains a solvent.

In the solvent removal process of (2), it is preferable to remove a solvent from the apply | coated film | membrane by pressure reduction (vacuum) and / or heating, and to form a dry coating film on a board | substrate.

In the exposure process of (3), it is preferable to irradiate actinic light of wavelength 300nm or more and 450nm or less to the obtained coating film. In this process, specific acid generators decompose and acid is generated. By the catalysis of the generated acid, the acid-decomposable group in the structural unit (a1) contained in the component A is decomposed to produce an acid group.

In order to accelerate said decomposition reaction in the area | region where an acid catalyst was produced, you may perform post-exposure heat processing: Post Exposure Bake (henceforth "PEB" hereafter) as needed. PEB can promote the production of acid groups from acid-decomposable groups.

The acid-decomposable group in the structural unit (a1) in the specific resin has a low activation energy for acid decomposition and is easily decomposed by an acid derived from a photoacid generator upon exposure to generate an acid group. Therefore, PEB is not necessarily performed. Therefore, it is preferable to perform the said developing process, without performing heat processing after an exposure process. More specifically, it is preferable to form a positive image by developing in the developing process of 4) without performing PEB after the exposure process of (3).

In addition, by performing PEB at a relatively low temperature, decomposition of the acid-decomposable group can be promoted without causing a crosslinking reaction. It is preferable that the temperature at the time of PEB is 30 degreeC or more and 130 degrees C or less, 40 degreeC or more and 110 degrees C or less are more preferable, 50 degreeC or more and 90 degrees C or less are especially preferable.

In the developing process of (4), it is preferable to develop the component A which has the free acidic radical, and the component B which has an acidic radical using alkaline developing solution. A positive image can be formed by removing the exposure part area | region containing the photosensitive resin composition which has an acidic radical which is easy to melt | dissolve in an alkaline developing solution.

By heating the positive image obtained in the post-baking process of (5), the acid group produced by thermally decomposing the acidic radical in the structural unit (b1), and the acid-decomposable group in the structural unit (a1), the structural unit (a2), and a structural unit, for example. A cured film can be formed by crosslinking with the crosslinkable group in (b2). It is preferable to heat this heating to 150 degreeC or more high temperature, It is more preferable to heat to 180-250 degreeC, It is especially preferable to heat to 200-250 degreeC. Although heating time can be set suitably according to heating temperature etc., it is preferable to set it in the range of 10 to 90 minutes.

The cured film obtained from the photosensitive resin composition of this invention can be used suitably as a dry etching resist.

When using the cured film obtained by thermosetting by the post-baking process of (5) as a dry etching resist, as an etching process, dry etching processes, such as ashing, plasma etching, and ozone etching, can be performed.

In the dry etching process of (6), well-known dryness, such as a reactive gas etching process which exposes a board | substrate in reaction gas, and performs etching, and reactive ion etching (RIE) which ionizes and radicalizes reaction gas by plasma, and performs etching. An etching process can be illustrated. What is necessary is just to select these gas species and an etching method suitably according to the material to dry-etch, desired speed, precision, etc. Moreover, a well-known apparatus can be used as an apparatus which performs dry etching.

In addition, it is preferable to include a step of exposing the entire surface of the developed photosensitive resin composition prior to the post-baking step, and if the step of totally irradiating actinic light, preferably ultraviolet rays, is added to the pattern of the developed photosensitive resin composition, irradiation of the actinic ray The acid generated by can accelerate the crosslinking reaction.

Next, the formation method of the cured film using the photosensitive resin composition of this invention is demonstrated concretely.

[Preparation Method of Photosensitive Resin Composition]

A solvent is mixed in the predetermined ratio and by arbitrary methods to the essential component of specific resin and an acid generator as needed, and it melt | dissolves and prepares the photosensitive resin composition. For example, after making specific resin or acid generator into the solution which melt | dissolved in the solvent, respectively, these can also be mixed in a predetermined ratio, and the photosensitive resin composition can also be prepared. The solution of the photosensitive resin composition prepared as mentioned above can also be used for use, after filtering using a filter etc. of 0.1 micrometer of pore diameters.

<Application process and solvent removal process>

A desired dry coating film can be formed by apply | coating the photosensitive resin composition to a predetermined board | substrate, and removing a solvent by pressure reduction and / or heating (prebaking). As said board | substrate, for example, in manufacture of a liquid crystal display device, the glass plate etc. which further formed the polarizing plate, the black matrix layer, the color filter layer as needed, and further formed the transparent conductive circuit layer can be illustrated. Although the coating method to a board | substrate is not specifically limited, Application | coating is preferable, For example, methods, such as a slit coat method, a spray method, a roll coat method, and a spin coating method, can be used. Among them, the slit coat method is preferable from the viewpoint of being suitable for large substrates. Here, a large board | substrate means the board | substrate of the magnitude | size whose each side is 1 m or more.

In addition, the heating conditions of (2) solvent removal process are the ranges in which an acid-decomposable group decomposes in the structural unit (a1) in the component A in an unexposed part, and does not make component A soluble in alkaline developing solution, Although it changes also with a kind and compounding ratio, Preferably it is about 30 to 300 second at 70-120 degreeC.

Exposure process

(3) In an exposure process, actinic light of a predetermined pattern is irradiated to the board | substrate which provided the dry coating film of the photosensitive resin composition. The exposure may be performed through a mask, or a predetermined pattern may be directly drawn. Active rays having a wavelength of 300 nm or more and 450 nm or less can be preferably used. You may perform PEB after an exposure process as needed.

A low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a chemical lamp, a laser generator, an LED light source, and the like can be used for exposure by an actinic ray.

When mercury lamps are commonly used, actinic rays having wavelengths such as g-ray (436 nm), i-ray (365 nm) and h-ray (405 nm) can be preferably used. Mercury lamps are preferred in that they are suitable for exposure to large areas as compared to lasers.

In the case of using a laser, 343 nm and 355 nm are preferably used in a solid state (YAG) laser, 351 nm (XeF) is preferably used in an excimer laser, and 375 nm and 405 nm are more preferably used in a semiconductor laser. Among these, 355 nm and 405 nm are more preferable from a viewpoint of stability, cost, etc. The laser can be irradiated to the coating film once or plural times. Moreover, about the specific example and preferable range of an energy density, pulse width, a laser frequency, an exposure apparatus, and a filter, the thing of Paragraph 0098-Paragraph 0100 of Unexamined-Japanese-Patent No. 2011-186398 is mentioned.

Development Process

(4) In the developing step, the exposure region is removed using a basic developer to form an image pattern. As a basic compound used for a developing solution, For example, alkali metal hydroxides, such as lithium hydroxide, sodium hydroxide, 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. Moreover, the aqueous solution which added an appropriate amount of water-soluble organic solvents, such as methanol and ethanol, and surfactant to the aqueous solution of the said alkalis can also be used as a developing solution.

The pH of the developer is not particularly limited as long as it can be developed, but is preferably 10.0 to 14.0.

The developing time is preferably 30 to 180 seconds, and the developing method may be any of a puddle method, a dipping method and a shower method. After development, flowing water can be washed for 10 to 90 seconds to form a desired pattern.

<Post Baking Process (Crosslinking Process)>

For a pattern corresponding to the unexposed region obtained by development, using a heating apparatus such as a hot plate or an oven at a predetermined temperature, for example, 180 to 250 ° C. for a predetermined time, for example, for 5 to 60 minutes In the oven, heat treatment is performed for 30 to 90 minutes to decompose an acid-decomposable group in a specific resin to generate a carboxyl group and / or phenolic hydroxyl group, to react with a crosslinkable group which is an epoxy group and / or oxetanyl group in the specific resin, and to crosslink it. A protective film or an interlayer insulating film excellent in hardness and the like can be formed. In addition, when performing heat processing, transparency can also be improved by performing in nitrogen atmosphere.

In addition, after re-exposure to actinic rays on the substrate on which the pattern is formed prior to the heat treatment, post-baking (re-exposure / post-baking) generates acid from the acid generator (B) present in the unexposed portion, thereby promoting crosslinking. It is preferable to function as a catalyst.

That is, it is preferable that the formation method of the cured film in this invention includes the process of re-exposing by actinic light between a developing process and a post-baking process.

Although exposure in a re-exposure process may be performed by the same means as the said exposure process, in the said re-exposure process, it is preferable to perform whole surface exposure to the side in which the film | membrane was formed by the photosensitive resin composition of this invention of a board | substrate. As a preferable exposure amount of a re-exposure process, it is 100-1,000mJ / cm <2>.

<Dry etching process>

The dry etching process in this invention is a process of performing dry etching with respect to the board | substrate which has a cured film obtained by thermosetting in the said post-baking process. Since the cured film obtained from the photosensitive resin composition of this invention is excellent in dry etching tolerance, even if it exposes to dry etching conditions, there is little film reduction amount.

The feed-etch etching materials that can be used in the present invention include silicon, silicon dioxide, silicon nitride, alumina, glass, glass-ceramic, gallium arsenide, indium phosphide, copper, aluminum, nickel, iron, steel, copper-silicon alloy, indium Tin oxide coated glass; Arbitrary substrates containing patterning regions of metals, semiconductors and insulating materials, and the like are included, but not limited thereto.

There is no restriction | limiting in particular as a generation method of plasma, Both a reduced pressure plasma method and an atmospheric plasma method can be apply | coated.

In the plasma etching, for example, inert gas selected from helium, argon, krypton, xenon, O ₂ , CF ₄ , C ₂ F ₄ , N ₂ , CO ₂ , SF ₆ , CHF ₃ , at least O, N, Reactive gases containing F or Cl can be preferably used.

In the dry etching step, for example, in the case of a silicon-based layer such as SiN _x or SiO ₂ , it is preferable to use a reactive gas such as O ₂ and fluorine such as CF ₄ or SiF ₆ .

In addition, the board | substrate in a dry etching process and the board | substrate in the said coating process may be the same, or may differ. For example, you may make the board | substrate in the said application process into a virtual board | substrate, and transfer the said cured film to another board | substrate before the said dry etching process.

Moreover, the cured film obtained by hardening | curing the photosensitive resin composition of this invention can be used suitably also as a sacrificial layer at the time of an etching process, such as dry etching and wet etching, and when it peels the said cured film after an etching process, known dry plasma, such as ashing, Peeling by known wet processes, such as a process and alkali chemicals treatment, can be performed. Since the cured film of this invention hardens | cures through a baking process, peeling by a dry plasma process is especially preferable.

Even when used as a planar resist as an etching resist, oxygen plasma treatment is preferably used, but it is also possible to peel off and remove the resist by heat treatment with a chemical solution.

The cured film obtained by hardening | curing the photosensitive resin composition of this invention can be used especially suitably as a dry etching resist.

The cured film of this invention is a cured film obtained by hardening | curing the photosensitive resin composition of this invention, and can be used suitably as an interlayer insulation film. Moreover, it is preferable that the cured film of this invention is a cured film obtained by the formation method of the cured film of this invention.

By the photosensitive resin composition of this invention, the cured film which has high sensitivity, the generation | occurrence | production of the residue at the time of image development is suppressed, and is excellent in smoothness is obtained, and the said cured film is useful as an interlayer insulation film. In addition, the interlayer insulating film formed by using the photosensitive resin composition of the present invention has high transparency, can form a pattern shape having a good shape, and is also excellent in smoothness of the surface thereof, and thus is suitable for use of an organic EL display device or a liquid crystal display device. useful.

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

For example, amorphous silicon TFT, low temperature polysilicon TFT, oxide semiconductor TFT etc. are mentioned as a specific example of TFT (Thin-Film Transistor) with which the organic electroluminescence display and liquid crystal display of this invention are equipped. Since the cured film of this invention is excellent in electrical characteristics, it can be used conveniently in combination with these TFT.

In addition, the liquid crystal display device of the present invention may be a twisted nematic (TN) method, a vertical alignment (VA) method, an in-place-switching (IPS) method, a frings field switching (FFS) method, or an OCB. (Optical Compensated Bend) method.

Moreover, the rubbing orientation method, photoalignment, etc. are mentioned as a specific orientation system of the liquid crystal aligning film which can take the liquid crystal display device of this invention. Furthermore, the polymer orientation may be supported by the PSA (Polymer Sustained Alignment) technique described in Japanese Patent Laid-Open No. 2003-149647 and Japanese Patent Laid-Open No. 2011-257734.

In addition, the photosensitive resin composition of this invention and the cured film of this invention can be used for various uses, without being limited to the said use. For example, in addition to the planarization film, the protective film, and the interlayer insulation film, a microlens provided on a color filter, a resist for etching, and a spacer for maintaining a constant thickness of the liquid crystal layer in a liquid crystal display device or a solid-state image sensor are particularly preferable. Preferably, it can be used suitably for a resist for dry etching.

1 shows a schematic conceptual view of an example of an organic EL display device using the photosensitive resin composition of the present invention. Typical sectional drawing of the board | substrate in a bottom emission type organic electroluminescence display is shown, and it has the planarization film 4. As shown in FIG.

It may form a bottom-gate type TFT (1), and comprising a state covering the TFT (1) to the Si ₃ N ₄ insulation film 3 is formed on the glass substrate 6. After forming a contact hole (not shown) in the insulating film 3, a wiring 2 (1.0 μm in height) connected to the TFT 1 through the contact hole is formed on the insulating film 3. The wiring 2 is for connecting the TFT 1 with the organic EL element formed between the TFTs 1 or in a later step.

In addition, in order to planarize the unevenness caused by the formation of the wiring 2, the flattening film 4 is formed on the insulating film 3 in a state of filling the unevenness by the wiring 2.

On the planarization film 4, the bottom emission type organic electroluminescent element is formed. That is, on the planarization film 4, the 1st electrode 5 which consists of ITO is connected to the wiring 2 through the contact hole 7, and is formed. The 1st electrode 5 is corresponded to the anode of organic electroluminescent element.

The insulating film 8 of the shape which covers the periphery of the 1st electrode 5 is formed, and by forming this insulating film 8, the short between the 1st electrode 5 and the 2nd electrode formed in a subsequent process is formed. You can prevent it.

In addition, although not shown in FIG. 1, the hole transport layer, the organic light emitting layer, and the electron transport layer are sequentially formed through a desired pattern mask, and a second electrode made of Al is formed on the entire surface above the substrate. It seals by sticking using a glass plate and an ultraviolet curable epoxy resin, and the active-matrix organic electroluminescent display apparatus by which the TFT 1 for driving this is connected to each organic electroluminescent element is obtained.

2 is a conceptual cross-sectional view showing an example of an active matrix liquid crystal display device 10. This color liquid crystal display device 10 is a liquid crystal panel having a backlight unit 12 on its back side, the liquid crystal panel comprising TFTs corresponding to all pixels disposed between two glass substrates 14 and 15 to which a polarizing film is attached. The element 16 is arranged. In each element formed on the glass substrate, the ITO transparent electrode 19 which forms a pixel electrode through the contact hole 18 formed in the cured film 17 is wired. On the ITO transparent electrode 19, the RGB color filter 22 which has arrange | positioned the layer of liquid crystal 20 and a black matrix is formed.

Example

Next, an Example demonstrates this invention further more concretely. However, this invention is not limited by these Examples. In addition, "part" and "%" are basis of weight unless there is particular notice.

&Lt; Synthesis Example 1 &

150 weight part of diethylene glycol ethylmethyl ether was put into the flask provided with the cooling tube and the stirrer, and it heated up at 90 degreeC under nitrogen atmosphere. 41.3 parts by weight of 1-ethoxyethyl methacrylate, 31.0 parts by weight of 3-ethyl-3-oxetanylmethyl methacrylate, 5.6 parts by weight of methacrylic acid, and 1ethyl 2-ethylhexyl methacrylate as monomer components in the solution. As a weight part and a polymerization initiator, 10.0 weight part of dimethyl-2,2'- azobis (2-methylpropionate) (made by Wako Pure Chemical) was melt | dissolved, and it dripped over 2 hours. It stirred for 2 hours after completion | finish of dripping. 2.5 parts by weight of dimethyl-2,2'-azobis (2-methylpropionate) was further added to the solution, followed by further stirring for 2 hours to terminate the reaction. This obtained copolymer A-1. The weight average molecular weight was 11,000.

<Synthesis example 2-38>

Except having changed the used monomer and its quantity, it carried out similarly to the synthesis example 1, and synthesize | combined the copolymer A-2-A-15, B-1-B-16, and b-1-b-5 which are shown in the following table, respectively. . The composition ratio (mol%) and weight average molecular weight (Mw) of each synthesize | combined copolymer are as showing in the following table.

The symbol of Table 1 and Table 2 is as follows.

MAEVE: Methacrylic acid 1-ethoxyethyl

MATHF: tetrahydro-2H-furan-2-yl methacrylate

MACHOE: 1- (cyclohexyloxy) ethyl methacrylate

MATHP: tetrahydro-2H-pyran-2-ylmethacrylate

PHSEVE: 1-ethoxyethyl group protector of p-hydroxystyrene

Oxe-30: 3-ethyl-3-oxetanylmethyl methacrylate (manufactured by Osaka Organic Chemical Industries, Ltd.)

GMA: glycidyl methacrylate

NBMA: n-butoxymethylacrylamide

VBGE: p-vinylbenzyl glycidyl ether

MAA: methacrylic acid

PHS: p-hydroxystyrene

HEMA: 2-ethylhexyl methacrylate

THFFMA: tetrahydrofurfuryl methacrylate

St: Styrene

α-MeSt: α-methylstyrene

MMA: methyl methacrylate

DCPM: Methacrylic acid (tricyclo [5.2.1.0 ^2,6 ] decane-8-yl)

(Examples 1-143 and Comparative Examples 1-34)

The amount (solid content) shown in the following table was dissolved in a mixed solvent of diethylene glycol methyl ethyl ether: propylene glycol monomethyl ether acetate = 1: 1 (weight ratio) so that the solid content concentration was 27% by weight, and the pore diameter was 0.2 m. It filtered by the membrane filter and prepared each photosensitive resin composition, respectively.

The symbol of the various additives in the said table is as follows.

C-1: compound (synthetic product) having the structure

C-2: compound (synthetic product) having the structure

C-3: the compound (synthetic product) of the following structure

C-4: CGI-1397 (made by BASF Corporation)

C-5: The compound of the following structure (it synthesize | combined according to the method of Paragraph 0108 of Unexamined-Japanese-Patent No. 2002-528451).

C-6: PAI-1001 (made by Midori Kagaku Co., Ltd.)

C-7: 4,7-di-n-butoxy-1-naphthyltetrahydrothiopheniumtrifluoromethanesulfonate

Synthesis of C-1

Aluminum chloride (10.6 g) and 2-chloropropionyl chloride (10.1 g) were added to a suspension solution of 2-naphthol (10 g) and chlorobenzene (30 mL), and the mixed solution was heated to 40 ° C and reacted for 2 hours. 4N HCl aqueous solution (60 mL) was dripped at the reaction liquid under ice cooling, ethyl acetate (50 mL) was added and liquid-separated. Potassium carbonate (19.2 g) was added to the organic layer, and the mixture was reacted at 40 DEG C for 1 hour, followed by separating an aqueous 2N HCl solution (60 mL). The organic layer was concentrated, and then crystallized with diisopropyl ether (10 mL), It filtered and dried and the ketone compound (6.5g) was obtained.

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

The obtained oxime compound (1.8 g) was dissolved in acetone (20 mL), triethylamine (1.5 g) and p-toluenesulfonyl chloride (2.4 g) were added under ice-cooling, and it heated up to room temperature and made it react for 1 hour. Water (50 mL) was added to the reaction solution, and the precipitated crystals were filtered off, reslurried with methanol (20 mL), filtered and dried to obtain C-1 (2.3 g).

In addition, the ¹ H-NMR spectrum (300 MHz, CDCl ₃ ) of B-1 shows δ = 8.3 (d, 1H), 8.0 (d, 2H), 7.9 (d, 1H), 7.8 (d, 1H), 7.6 (dd, 1H), 7.4 (dd, 1H), 7.3 (d, 2H), 7.1 (d. 1H), 5.6 (q, 1H), 2.4 (s, 3H), and 1.7 (d, 3H).

Synthesis of C-2

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

Sodium acetate (30.6 g), hydroxylamine hydrochloride (25.9 g), and magnesium sulfate (4.5 g) were added to the obtained ketone compound (10.0 g) and the suspension solution of methanol (100 mL), and it heated and refluxed for 24 hours. After cooling, water (150 mL) and ethyl acetate (150 mL) were added and the mixture was separated. The organic layer was separated four times with 80 mL of water, concentrated, and purified by silica gel column chromatography to obtain an oxime compound (5.8 g).

The obtained oxime (3.1 g) was sulfonated similarly to C-1, and C-2 (3.2 g) was obtained.

In addition, the ¹ H-NMR spectrum (300MHz, CDCl ₃ ) of B-2 is δ = 8.3 (d, 1H), 8.0 (d, 2H), 7.9 (d, 1H), 7.8 (d, 1H), 7.6 (dd, 1H), 7.5 (dd, 1H) 7.3 (d, 2H), 7.1 (d.1H), 5.6 (dd, 1H), 2.4 (s, 3H), 2.2 (ddt, 1H), 1.9 (ddt , 1H), 1.4 to 1.2 (m, 8H), and 0.8 (t, 3H).

Synthesis of C-3

C-3 was synthesize | combined similarly to C-1 except having used benzenesulfonyl chloride instead of p-toluenesulfonyl chloride in C-1.

In addition, C-1's ¹ H-NMR spectrum (300 MHz, CDCl ³ ) is δ = 8.3 (d, 1H), 8.1 (d, 2H), 7.9 (d, 1H), 7.8 (d, 1H), 7.7 -7.5 (m, 4H), 7.4 (dd, 1H), 7.1 (d. 1H), 5.6 (q, 1H), and 1.7 (d, 3H).

D-1: DBA (9,10-dibutoxy anthracene and the Kawasaki Kasei Co., Ltd. product)

E-1: 1,5-diazabicyclo [4,3,0] -5-nonene (made by Tokyo Kasei Kogyo Co., Ltd.)

E-2: compound of the structure

S-1: the following compound (manufacturer: Shin-Etsu Chemical Co., Ltd., article number: KBE-3026)

S-6: the following compound (manufacturer: Toray Dow Co., Ltd., part number: Z6920)

S-7: the following compound (manufacturer: Shin-Etsu Chemical Co., Ltd., part number: KBE-846)

S-8: the following compound (manufacturer: Shin-Etsu Chemical Co., Ltd., article number: KBM-9659)

F-1: JER150S65 (made by Mitsubishi Kagaku Co., Ltd.)

F-2: JER1031S (made by Mitsubishi Kagaku Co., Ltd.)

G-1: 3-glycidoxy propyl trimethoxysilane (KBM-403, Shin-Etsu Chemical Co., Ltd. make)

H-1: the compound of

<Evaluation of chemical resistance (peel resistance)>

After slit-coating each photosensitive resin composition on a glass substrate (Corning 1737, 0.7 mm thickness (made by Corning)), a solvent is removed by heating on a 90 degreeC / 120 second hotplate, and the photosensitive resin composition layer of 4.0 micrometers of film thicknesses is carried out. Formed.

The obtained photosensitive resin composition layer was exposed to a total irradiation amount of 300 mJ / cm 2 (energy intensity: 20 kW / cm 2, i-line) with a PLA-501F exposure machine (ultra high pressure mercury lamp) manufactured by Canon Corporation, and then the substrate was exposed to an oven. Heated at 230 ° C. for 1 hour to obtain a cured film.

The cured film was immersed in monoethanolamine at 60 degreeC for 5 minutes, and the film thickness was measured immediately after lifting up the film | membrane and wiping off the surface liquid. The ratio which increased the film thickness before immersion and the film thickness after immersion was expressed in percentage. The results are shown in the table below. The smaller the numerical value, the better the peeling liquid resistance of the cured film, and A or B is preferable.

Swelling rate (%) = film thickness (micrometer) after immersion / film thickness (micrometer) before immersion x 100

A: 100% or more but less than 102%

B: 102% or more but less than 105%

C: 105% or more but less than 110%

D: 110% or more but less than 115%

E: 115% or more

<Evaluation of chemical resistance (NMP resistance)>

After slit-coating each photosensitive resin composition on a glass substrate (Corning 1737, 0.7 mm thickness (made by Corning)), the solvent was removed by heating on a 90 degreeC / 120 second hotplate, and the photosensitive resin composition layer of 4.0 micrometers of film thicknesses was removed. Formed.

The obtained photosensitive resin composition layer was exposed to a total irradiation amount of 300 mJ / cm 2 (energy intensity: 20 kW / cm 2, i-line) with a PLA-501F exposure machine (ultra high pressure mercury lamp) manufactured by Canon Corporation, and then the substrate was exposed to an oven. Heated at 230 ° C. for 1 hour to obtain a cured film.

The cured film was immersed in NMP for 10 minutes at 80 degreeC, the film thickness was measured immediately after pulling up the film and wiping off the liquid on the surface. The ratio which increased the film thickness before immersion and the film thickness after immersion was expressed in percentage. The results are shown in the table below. As numerical value is small, NMP tolerance of a cured film is favorable, and A or B is preferable.

Swelling rate (%) = film thickness after immersion (µm) / film thickness before immersion (µm) x 100

A: 100% or more but less than 102%

B: 102% or more but less than 105%

C: 105% or more but less than 110%

D: 110% or more but less than 115%

E: 115% or more

<Dry etching resistance>

After slit-coating each photosensitive resin composition on a glass substrate (Corning 1737, 0.7 mm thickness (made by Corning Corporation)), a solvent is removed by heating on a 90 degreeC / 120 second hotplate, and the photosensitive resin composition layer of 4.0 micrometers of film thicknesses is carried out. Formed.

The obtained photosensitive resin composition layer was exposed to a total irradiation amount of 300 mJ / cm 2 (energy intensity: 20 kW / cm 2, i-line) with a PLA-501F exposure machine (ultra high pressure mercury lamp) manufactured by Canon Corporation, and then the substrate was exposed to an oven. Heated at 230 ° C. for 1 hour to obtain a cured film. Dry etching the cured film under the conditions of CF ₄ 50 ml / min, O ₂ 10 ml / min, output 400 kPa, etching time 90 seconds using an etching gas using a dry etching apparatus "CDE-80N (manufactured by Shibaura Mechatronics)". Done. The etching rate was calculated from the film reduction amount. The smaller the numerical value, the higher the dry etching resistance, and A or B is preferable.

A: 30 ms / sec or more and less than 35 ms / sec

B: 35 ms / sec or more and less than 40 ms / sec

C: 40 ms / sec or more but less than 45 ms / sec

&Lt; Example 144 >

In the active-matrix liquid crystal display device of FIG. 1 of Unexamined-Japanese-Patent No. 3321003, the cured film 17 was formed as an interlayer insulation film as follows, and the liquid crystal display device of Example 144 was obtained. That is, the cured film 17 was formed as an interlayer insulation film using the photosensitive resin composition of Example 1.

That is, the substrate was exposed for 30 seconds under hexamethyldisilazane (HMDS) vapor as a pretreatment for improving the wettability of the substrate of paragraph 58 of Japanese Patent No. 3321003 and the interlayer insulating film 17, and then carried out. After spin-coating the photosensitive resin composition of Example 1, it prebaked at 90 degreeC for 2 minutes on a hotplate, the solvent was volatilized, and the photosensitive resin composition layer with a film thickness of 3 micrometers was formed. Subsequently, the obtained photosensitive resin composition layer was exposed to 40 mJ / cm 2 (energy intensity: 20 kW / cm 2, i-line) through a mask of a hole pattern of 10 μmφ using Canon MPA 5500CF (high pressure mercury lamp). did. And after developing the photosensitive resin composition layer after exposure for 23 degreeC / 60 second with alkaline developing solution (0.4% of tetramethylammonium hydroxide aqueous solution), it rinsed with ultrapure water for 20 second. Subsequently, the total exposure was performed so that the accumulated irradiation amount might be 300 mJ / cm 2 (energy intensity: 20 kW / cm 2, i-line) using an ultrahigh pressure mercury lamp, and then the substrate was heated at 230 ° C. for 30 minutes in an oven to obtain a cured film.

The applicability | paintability at the time of apply | coating the said photosensitive resin composition was favorable, and generation | occurrence | production of a wrinkle and a crack was not recognized in the cured film obtained after exposure, image development, and baking.

As a result of applying a drive voltage to the obtained liquid crystal display device, it showed favorable display characteristics, and it turned out that it is a highly reliable liquid crystal display device.

<Example 145>

Only Example 144 and the following processes were changed and the same liquid crystal display device was obtained. That is, even when the hexamethyldisilazane (HMDS) process which is a board | substrate pretreatment was abbreviate | omitted and the photosensitive resin composition of Example 52 was apply | coated, it was a favorable state without the defect of a pattern and peeling as an obtained cured film. Moreover, the performance as a liquid crystal display device was also favorable similarly to Example 144. This is considered to be because the composition of this invention is excellent in adhesiveness with a board | substrate. It is also preferable to omit the process of the said substrate pretreatment from a viewpoint of improving productivity.

<Example 146>

Only Example 144 and the following processes were changed and the same liquid crystal display device was obtained. That is, even if it changed alkaline developing solution from 0.4% of tetramethylammonium hydroxide aqueous solution to 2.38% of tetramethylammonium hydroxide aqueous solution, it was a favorable state without the defect of a pattern and peeling as an obtained cured film. Moreover, the performance as a liquid crystal display device was also favorable similarly to Example 144. This is considered to be because the composition of this invention is excellent in adhesiveness with a board | substrate.

<Example 147>

Only Example 144 and the following processes were changed and the same liquid crystal display device was obtained. That is, even if it changed alkaline developing solution into 0.04% of KOH aqueous solution from 0.4% of tetramethylammonium hydroxide aqueous solution, it was a favorable state without the defect of a pattern and peeling as an obtained cured film. Moreover, the performance as a liquid crystal display device was also favorable similarly to Example 144. This is considered to be because the composition of this invention is excellent in adhesiveness with a board | substrate.

<Example 148>

Only Example 144 and the following processes were changed and the same liquid crystal display device was obtained. That is, the process of the front surface exposure after image development and rinsing was abbreviate | omitted, and it heated at 230 degreeC in oven for 30 minutes, and obtained the cured film. The performance as an obtained liquid crystal display device was favorable similarly to Example 144. This is considered to be because the composition of the present invention is excellent in drug resistance. It is also preferable to omit the process of whole surface exposure from a viewpoint of improving productivity.

<Example 149>

Only Example 144 and the following processes were changed and the same liquid crystal display device was obtained. That is, the process of heating on a 3-minute hotplate at 100 degreeC between the process of whole surface exposure and the 230 degreeC / 30-minute heating process in oven was added. The performance as an obtained liquid crystal display device was favorable similarly to Example 149. It is also preferable to add this process from a viewpoint of having the shape of a hole pattern.

<Example 150>

Only Example 144 and the following processes were changed and the same liquid crystal display device was obtained. That is, the process heated on a 3-minute hotplate at 100 degreeC between the process of image development and rinsing and the front exposure was added. The performance as an obtained liquid crystal display device was favorable similarly to Example 144. It is also preferable to add this process from a viewpoint of having the shape of a hole pattern.

<Example 151>

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

A glass substrate 6, the insulating film 3 made of Si ₃ N ₄ forming a TFT (1) of the bottom gate type on, and in a state covering the TFT (1) was formed. Subsequently, a contact hole (not shown here) was formed in the insulating film 3, and then a wiring 2 (1.0 μm in height) connected to the TFT 1 through the contact hole was formed on the insulating film 3. . This wiring 2 is for connecting the TFT 1 with the organic EL element formed between the TFTs 1 or in a later step.

In addition, in order to planarize the unevenness caused by the formation of the wiring 2, the planarization layer 4 was formed on the insulating film 3 in a state of filling the unevenness of the wiring 2. Formation of the planarization film 4 onto the insulating film 3 is performed by spin-coating the photosensitive resin composition of Example 1 on a substrate, prebaking on a hot plate (90 ° C. × 2 minutes), and then applying a high pressure mercury lamp onto a mask. After irradiating i-ray (365nm) with 45mJ / cm2 (energy intensity 20㎽ / ㎠), it is developed with alkaline aqueous solution (0.4% TMAH aqueous solution) to form a pattern. (Energy intensity: 20 kW / cm <2>, i line | wire), it exposed all over and heat-processed for 60 minutes at 230 degreeC. The applicability | paintability at the time of apply | coating the said photosensitive resin composition was favorable, and generation | occurrence | production of a wrinkle and a crack was not recognized in the cured film obtained after exposure, image development, and baking. Moreover, the film thickness of the planarization film 4 which produced 500 nm of average level | step differences of the wiring 2 was 2,000 nm.

Subsequently, a bottom emission type organic EL device was formed on the obtained planarization film 4. First, on the planarization film 4, the 1st electrode 5 which consists of ITO was connected to the wiring 2 through the contact hole 7, and was formed. Then, the resist was apply | coated and prebaked, and it exposed and developed through the mask of a desired pattern. Using this resist pattern as a mask, pattern processing was performed by wet etching using ITO etchant. Then, the said resist pattern was stripped using the resist stripping liquid (mixed liquid of monoethanolamine and dimethyl sulfoxide (DMSO)). The 1st electrode 5 obtained in this way is corresponded to the anode of organic electroluminescent element.

Next, the insulating film 8 of the shape which covers the periphery of the 1st electrode 5 was formed. The insulating film 8 was formed in the insulating film by the method similar to the above using the photosensitive resin composition of Example 3. As shown in FIG. By forming this insulating film, the short between the 1st electrode 5 and the 2nd electrode formed in a subsequent process can be prevented.

Further, the hole transport layer, the organic light emitting layer, and the electron transport layer were sequentially deposited in a vacuum deposition apparatus via a desired pattern mask. Next, the 2nd electrode which consists of Al in the whole surface above a board | substrate was formed. The obtained said board | substrate was taken out from the vapor deposition machine, and it sealed by sticking using the sealing glass plate and an ultraviolet curable epoxy resin.

As described above, an active matrix organic EL display device obtained by connecting the TFT 1 for driving this to each organic EL element was obtained. As a result of applying a voltage through the driving circuit, it was found that the display device exhibited good display characteristics and was a highly reliable organic EL display device.

Example 152

In Example 144, except having replaced the photosensitive resin composition of Example 1 with the photosensitive resin composition of Example 16, the liquid crystal display device was similarly produced. It showed that favorable display characteristics were shown and it was a highly reliable liquid crystal display device.

<Example 153>

In Example 144, a liquid crystal display device was produced in a similar manner except that the photosensitive resin composition of Example 1 was replaced with the photosensitive resin composition of Example 31. It showed that favorable display characteristics were shown and it was a highly reliable liquid crystal display device.

<Example 154>

In Example 144, except having replaced the photosensitive resin composition of Example 1 with the photosensitive resin composition of Example 132, the organic EL apparatus was produced similarly. It showed that favorable display characteristics were shown and it was a highly reliable organic electroluminescent display apparatus.

<Example 155>

In Example 151, the organic EL device was similarly manufactured except having replaced the photosensitive resin composition of Example 1 with the photosensitive resin composition of Example 16. It showed that favorable display characteristics were shown and it was a highly reliable organic electroluminescent display apparatus.

<Example 156>

In Example 151, the organic EL device was similarly manufactured except having replaced the photosensitive resin composition of Example 1 with the photosensitive resin composition of Example 31. It showed that favorable display characteristics were shown and it was a highly reliable organic electroluminescent display apparatus.

<Example 157>

In Example 151, the organic EL device was similarly manufactured except having replaced the photosensitive resin composition of Example 1 with the photosensitive resin composition of Example 133. It showed that favorable display characteristics were shown and it was a highly reliable organic electroluminescent display apparatus.

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: cured film 18: contact hole
19: ITO transparent electrode 20: liquid crystal
22: color filter

Claims (19)

(Component A) a polymer component comprising a polymer which satisfies at least one of the following (1) and (2),
(1) (a1) the acid group has a polymer having a structural unit having a group protected with an acid-decomposable group and (a2) a crosslinkable group,
(2) the acid group (a1) has a polymer having 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 C) a photoacid generator, and
(Component D) contains a solvent, and
(Component X) The positive photosensitive resin composition containing the silicon compound which has two or more hydrolyzable silyl groups and / or silanol groups represented by Formula (X1) in 1 molecule.

[In the formula, at least one of R ^X1 to R ^X3 is a hydrolyzable group selected from the group consisting of alkoxy group, mercapto group, halogen atom, amide group, acetoxy group, amino group, allyloxy group and isopropenoxy group or Represents a hydroxyl group. The remaining R ^X1 to R ^X3 each independently represent a hydrogen atom, a halogen atom or a monovalent organic substituent] The method of claim 1,
At least two of R <^X1> -R <^X3> is an alkoxy group in the said structural unit (X1), The positive photosensitive resin composition characterized by the above-mentioned. 3. The method according to claim 1 or 2,
Positive component photosensitive resin composition characterized by the above-mentioned component X being 0.1 weight% or more with respect to the sum total of the component except the solvent of the resin composition. 3. The method according to claim 1 or 2,
The positive photosensitive resin composition, wherein the structural unit (a1) is a structural unit having a residue in which a carboxyl group is protected by acetal or ketal. 3. The method according to claim 1 or 2,
The said structural unit (a1) is a structural unit represented by Formula (a1-1), The positive photosensitive resin composition characterized by the above-mentioned.

[Wherein R ¹ and R ² each represent a hydrogen atom, an alkyl group or an aryl group, at least one of R ¹ and R ² is an alkyl group or an aryl group, R ³ represents an alkyl group or an aryl group, and R ¹ or R ² and R ³ may be linked 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] 3. The method according to claim 1 or 2,
At least 2 of R <^X1> -R <^X3> of the said structural unit (X1) is a methoxy group or an ethoxy group, The positive photosensitive resin composition characterized by the above-mentioned. 3. The method according to claim 1 or 2,
The said structural unit (a2) is a positive photosensitive resin composition characterized by the above-mentioned structural unit which has at least 1 sort (s) chosen from an epoxy group and an oxetanyl group. 3. The method according to claim 1 or 2,
The weight ratio of the content W _A of the component _A and the content W _B of the component B is W _A / W _B = 98/2 to 20/80, wherein the positive photosensitive resin composition is used. 3. The method according to claim 1 or 2,
Said component C is an oxime sulfonate compound which has at least 1 of an oxime sulfonate residue represented by Formula (c0), The positive photosensitive resin composition characterized by the above-mentioned.

3. The method according to claim 1 or 2,
At least two of R <^X1> -R <^X3> is an alkoxy group in the said structural unit (X1), and content of the said component X is 0.1 weight% or more with respect to the sum total of the component except the solvent of a resin composition, Positive type photosensitive resin Composition. 3. The method according to claim 1 or 2,
Positive type characterized in that at least two of R ^X1 to R ^X3 in the structural unit (X1) is an alkoxy group, and at least two of R ^X1 to R ^X3 in the structural unit (X1) is a methoxy group or an ethoxy group. Photosensitive resin composition. 3. The method according to claim 1 or 2,
At least 2 of R <^X1> -R <^X3> is an alkoxy group in the said structural unit (X1), and content of the said component X is 0.1 weight% or more with respect to the sum total of the component except the solvent of a resin composition, The said structural unit (X1) At least two of R <^X1> -R <^X3> is a methoxy group or an ethoxy group, The positive photosensitive resin composition characterized by the above-mentioned. (1) Process of apply | coating positive type photosensitive resin composition of Claim 1 on board | substrate,
(2) removing the solvent from the applied photosensitive resin composition,
(3) Process of exposing photosensitive resin composition from which solvent was removed by actinic light,
(4) process of developing exposed photosensitive resin composition with aqueous developing solution, and
(5) The post-baking process of thermosetting the developed photosensitive resin composition, The formation method of the cured film characterized by the above-mentioned. The method of claim 13,
And a step of exposing the entire surface of the photosensitive resin composition developed after the developing step and before the post-baking step. The method according to claim 13 or 14,
(6) The method of forming a cured film, further comprising the step of performing dry etching with respect to the board | substrate which has a cured film obtained by thermosetting. It was formed by the formation method of the cured film of Claim 13, The cured film characterized by the above-mentioned. 17. The method of claim 16,
It is an interlayer insulation film, The cured film characterized by the above-mentioned. The cured film of Claim 16 is provided, The organic electroluminescence display characterized by the above-mentioned. The cured film of Claim 16 is provided, The liquid crystal display device characterized by the above-mentioned.

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