KR20130035211A - Photosensitive curable resin composition, cured film and method for the cured film - Google Patents

Abstract

PURPOSE: A photosensitive resin composition, a method of manufacturing hardening film, organic EL displaying device or liquid crystal display is provided to be high-sensitive, stable in storing, be chemical resistant, high in exposure margin or development margin and ITP sputter resistant. CONSTITUTION: A photosensitive resin composition comprises a polymer component, a compound comprising an oxime sulfonate group which is represented as chemical structure b1. The polymer component comprises a monomer structure which is repetitive and includes carboxy group, a monomer group(a1) which is repetitive and includes a phenolic -OH group which is surrounded by an acid dissolution, a structure unit(a2) comprising a cross linking group in the same or the similar polymer. The solvent contains more than one solvent of which boiling point is below 180>= and more than one solvent of which boiling point is over 180>=. The ratio of total amount of the solvent below 180>= to the total amount of the solvent over 180>= is 99:1~50:5 after weight conversion. The chemical structure b1 has R5 which is represented as an alkyl group or an aryl group.

Description

Photosensitive resin composition, cured film, and its manufacturing method {PHOTOSENSITIVE CURABLE RESIN COMPOSITION, CURED FILM AND METHOD FOR THE CURED FILM}

This invention relates to the photosensitive resin composition, a cured film, and its manufacturing method. Moreover, it is related with electronic devices, such as an organic electroluminescence display using the said cured film, and a liquid crystal display. More specifically, the positive photosensitive resin composition suitable for formation of the planarization film | membrane of electronic components, such as an organic electroluminescence display, a liquid crystal display device, an integrated circuit element, a solid-state image sensor, a protective film, and an interlayer insulation film, and its use It relates to a method for producing a cured film.

In an organic EL display device, a liquid crystal display device, or the like, a patterned interlayer insulating film is generally provided to insulate between wirings arranged in layers. In the formation of this interlayer insulating film, the number of steps for obtaining the required pattern shape is small, and it is preferable to have sufficient flatness. Therefore, the photosensitive resin composition is widely used.

Highly reliable cured film, such as an interlayer insulating film or a planarization film formed by using the photosensitive resin composition as described above, in addition to transparency, excellent in solvent resistance and resistance to indium tin oxide (ITO) sputtered on the upper layer. It is required to be.

In recent years, high resolution of the photosensitive resin composition is calculated | required in order to make an organic electroluminescence display and a liquid crystal display device high-definition display characteristics.

Here, as a photosensitive resin composition, the thing of Unexamined-Japanese-Patent No. 2004-264623 is known. Moreover, the solvent used for the photosensitive resin composition is widely examined until now, For example, the chemically amplified positive resist composition which can form the resist pattern with a large unexposed part residual film rate is proposed (for example, Japanese Unexamined Patent Publication 2001). -56558).

However, the inventors of the present application have studied Japanese Patent Application Laid-Open No. 2004-264623 and Japanese Patent Application Laid-Open No. 2001-56558, and these compositions have high sensitivity, are excellent in storage stability, and have the reliability (especially chemical resistance) of the cured film obtained. It turned out that it is excellent and that the exposure margin and image development margin at the time of manufacture of a cured film are not a wide photosensitive resin composition. In addition, when ITO is provided on the surface of the photosensitive composition by sputtering or the like, resistance to this is also required. The present invention aims to solve these problems, and has high sensitivity, excellent storage stability, excellent reliability (especially chemical resistance) of the resulting cured film, wide exposure margin and developing margin in the production of cured film, and ITO. It aims at providing the photosensitive resin composition etc. which were excellent in sputter resistance. Moreover, it aims at providing the photosensitive resin composition which has tolerance (Hereinafter, it may be called "ITO sputter resistance") when providing ITO by sputtering etc.

As a result of earnestly examining by this inventor under such a situation, in the photosensitive resin composition, 6, the boiling point of the solvent below 180 degreeC, and the 180 degreeC or more solvent are used as a solvent component (the total amount of a boiling point below 180 degreeC): It discovered that the said subject can be solved by using it in ratio so that (a total amount of solvent of boiling point 180 degreeC or more) may be 99: 1-50: 50.

Specifically, by the following means (1), (7), (9) or (11) or less, Preferably, by means of the following (2)-(6), (8) and (10) The above object was achieved.

<1> (A) the repeating unit derived from the monomer which has a carboxyl group protected by the acid-decomposable group, and / or the repeating unit (a1) derived from the monomer which has a phenolic hydroxyl group protected by the acid-decomposable group, and the structural unit which has a crosslinking group ( a polymer component containing a2) in the same polymer and / or different polymer,

(B) a compound containing an oxime sulfonate residue represented by the following general formula (b1), and

(In General Formula (b1), R ⁵ represents an alkyl group or an aryl group.)

(C) It contains a solvent, As said solvent, At least 1 type of boiling point contains the solvent below 180 degreeC, At least 1 type of boiling point contains the solvent above 180 degreeC, and (The boiling point is a total amount of the solvent below 180 degreeC). : Photosensitive resin composition whose (boiling point total amount of solvent 180 degreeC or more) is 99: 1-50: 50 in mass conversion.

The photosensitive resin composition as described in <1> whose <2> above-mentioned boiling point has a distribution coefficient (LogP) of 180 degreeC or more solvent of -0.5-1.0.

<3> A compound containing the (B) oxime sulfonate moiety, consisting of the following general formula (OS-3), general formula (OS-4), general formula (OS-5), and general formula (b2). The photosensitive resin composition as described in <1> or <2> containing at least 1 sort (s) chosen from a group.

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

(In general formula (b2), R <^5> represents an alkyl group or an aryl group, X represents an alkyl group, an alkoxy group, or a halogen atom, m represents the integer of 0-3, when m is 2 or 3, it is a plurality X may be same or different.)

<4> The repeating unit (a2) derived from the monomer which has the said crosslinking group contains at least 1 sort (s) chosen from the group which consists of a 3-membered ring and / or 4-membered cyclic ether residue, and an ethylenically unsaturated group. The photosensitive resin composition in any one of 1>-<3>.

<5> Photosensitive resin composition in any one of <1>-<4> containing (E) epoxy resin further.

The photosensitive resin composition in any one of <1>-<5> which is a <6> chemically amplified positive type photosensitive resin composition.

<7> (1) Process of applying the photosensitive resin composition in any one of <1>-<6> on a board | substrate,

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

(3) exposing to active radiation;

(4) developing with a developing solution, and

(5) A method of forming a cured film, comprising the step of thermosetting.

<8> The method for forming a cured film according to <7>, which includes a step of exposing the entire surface after the developing step and before the step of thermosetting.

<9> Cured film formed by the formation method as described in <7> or <8>.

The cured film as described in <9> which is a <10> interlayer insulation film.

<11> The organic electroluminescence display or liquid crystal display device containing the cured film as described in <9> or <10>.

According to the present invention, there is provided a photosensitive resin composition having high sensitivity, excellent storage stability, excellent reliability (particularly chemical resistance) of the resulting cured film, wide exposure margin and development margin at the time of cured film production, and excellent ITO sputter resistance. It is possible to do

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.

EMBODIMENT OF THE INVENTION Below, the content of this invention is demonstrated in detail. In addition, it is used by the meaning which includes with "-" the numerical value described before and after that as a lower limit and an upper limit in this specification. In this specification, unless otherwise indicated, "group", such as an alkyl group, may have a substituent, and does not need to have it. In addition, in the case of group in which carbon number is limited, the said carbon number means the number containing the carbon number which a substituent has. In addition, an organic electroluminescent element means an organic electroluminescent element.

The photosensitive resin composition of this invention crosslinks with the repeating unit (a1) derived from the monomer which has a (A) repeating unit derived from the monomer which has a carboxyl group protected by the acid-decomposable group, and / or the phenolic hydroxyl group protected by the acid-decomposable group, A copolymer having a repeating unit (a2) derived from a monomer having a group, (B) a compound containing an oxime sulfonate residue represented by the following general formula (b1), and (C) a solvent, and containing at least as a solvent One boiling point contains a solvent of less than 180 ° C. and at least one boiling point of a solvent of 180 ° C. or more (the total amount of the solvent having a boiling point of less than 180 ° C.): (the total amount of the solvent having a boiling point of 180 ° C. or more) is 99: It is characterized by 1 to 50:50.

(In General Formula (b1), R ⁵ represents an alkyl group or an aryl group.)

By setting it as such a structure, the photosensitive resin composition excellent in all of a sensitivity, storage stability, solvent resistance, and exposure margin can be obtained.

Since such photosensitive resin composition is post-baked to some extent with the solvent remaining in a film | membrane, a crosslinking reaction is more easy to be accelerated | stimulated, a dense film can be formed, and ITO sputter resistance can be considered that it improves.

Hereinafter, the photosensitive resin composition of this invention is demonstrated in detail.

(A) Polymer

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 by an acid-decomposable group and (a2) a crosslinking group, and (2) an (a1) acid group At least one of a polymer having a structural unit having a moiety protected with an acid-decomposable group and a polymer having a structural unit having a crosslinkable group (a2). Moreover, you may contain polymers other than these. In addition to said (1) and / or (2), the (A) polymer component (henceforth "(A) component" hereafter) in this invention is added as needed, unless it mentions specially. It means containing a polymer.

The component (A) may contain other monomer units (a3) in addition to the monomer units (a1) and monomer units (a2).

In the present invention, a repeating unit derived from a monomer having a carboxyl group protected with an acid-decomposable group is preferred among the repeating units derived from a monomer having a carboxyl group protected with an acid-decomposable group and a monomer derived from a monomer having a phenolic hydroxyl group protected with an acid-decomposable group. Do.

It is preferable that (A) copolymer is alkali insoluble and becomes resin which becomes alkali-soluble when the acid-decomposable group which monomer unit (a1) has decomposed. Here, an acid-decomposable group means the functional group which can decompose in presence of an acid. That is, the repeating unit derived from the monomer which has a carboxyl group protected by the acid-decomposable group can produce | generate a carboxyl group by decomposing a protecting group with an acid, and the repeating unit derived from the monomer which has a phenolic hydroxyl group protected by the acid-decomposable group is When a protecting group decomposes | dissolves with an acid, a phenolic hydroxyl group can be produced | generated. Here, in this invention, "alkali-soluble" is 23 degreeC of the coating film (3 micrometers in thickness) of the said compound (resin) formed by apply | coating the solution of the said compound (resin) on a board | substrate, and heating at 90 degreeC for 2 minutes. The dissolution rate in the 0.4% tetramethylammonium hydroxide aqueous solution in the solution is 0.01 µm / sec or more, and the term “alkali insoluble” is applied by applying a solution of the compound (resin) onto a substrate and heating at 90 ° C. for 2 minutes. It says that the dissolution rate with respect to the 0.4% tetramethylammonium hydroxide aqueous solution in 23 degreeC of the coating film (3 micrometers in thickness) of the said compound (resin) formed is less than 0.01 micrometer / sec.

The said (A) copolymer does not exclude introduction | transduction of an acidic group, as long as the said (A) copolymer is maintained as alkali insoluble, but has the carboxy group, carboxylic anhydride residue, and / or phenolic hydroxyl group mentioned later You may have a monomeric unit.

It is preferable that (A) copolymer is addition polymerization type resin, and is a polymer which contains the monomer unit derived from (meth) acrylic acid and / or its ester as a main component. Moreover, the monomer derived from monomer units other than the monomer unit derived from (meth) acrylic acid and / or its ester, for example, the monomer unit derived from styrene, and a vinyl compound within the range which does not deviate from the meaning of this invention. You may have a unit etc.

It is preferable that the said (A) copolymer contains 50 mol% or more of the monomer unit derived from (meth) acrylic acid and / or its ester with respect to all the monomer units in a polymer, and contains 90 mol% or more It is more preferable, and it is especially preferable that it is a polymer which consists only of the monomeric unit derived from (meth) acrylic acid and / or its ester.

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

Hereinafter, the monomer unit (a1) and the monomer unit (a2) will be described.

(a1) Repeating unit derived from the monomer which has a carboxyl group protected by acid-decomposable group, or repeating unit derived from the monomer which has phenolic hydroxyl group protected by acid-decomposable group

The component (A) has a repeating unit derived from a monomer having a carboxyl group protected with an acid-decomposable group, or a repeating unit derived from a monomer having a phenolic hydroxyl group protected with an acid-decomposable group. When (A) component has a monomer unit (a1), it can be set as the very highly sensitive photosensitive resin composition.

(a1-1) Repeating unit derived from a monomer having a carboxyl group protected by an acid-decomposable group

(a1-1-1) Monomer unit having a carboxyl group

As a monomeric unit which has a carboxyl group, the monomeric unit derived from unsaturated carboxylic acid etc. which have at least 1 carboxyl group in a molecule | numerator, such as unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, and unsaturated tricarboxylic acid, is mentioned, for example.

As unsaturated carboxylic acid used in order to obtain the monomeric unit which has a carboxyl group, the following can be used. That is, as unsaturated monocarboxylic acid, acrylic acid, methacrylic acid, crotonic acid, (alpha)-chloroacrylic acid, cinnamic acid etc. are mentioned, for example. Moreover, as unsaturated dicarboxylic acid, a maleic acid, a fumaric acid, itaconic acid, a citraconic acid, a mesaconic acid, etc. are mentioned, for example. Moreover, the acid anhydride may be sufficient as unsaturated polyhydric carboxylic acid used in order to obtain the monomeric unit which has a carboxyl group. Specifically, maleic anhydride, itaconic anhydride, citraconic anhydride, etc. are mentioned. In addition, the unsaturated polyhydric carboxylic acid may be mono (2-methacryloyloxyalkyl) ester of polyhydric carboxylic acid, for example, monosuccinate mono (2-acryloyloxyethyl) and monosuccinate mono (2-methacryloyloxy Ethyl), mono phthalate (2-acryloyloxyethyl), mono phthalate (2-methacryloyloxyethyl), 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. Can be mentioned.

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 monomer unit which has a carboxyl group from a developable viewpoint, it is preferable to use acrylic acid, methacrylic acid, or anhydride of unsaturated polyhydric carboxylic acid, etc., and it is more preferable to use acrylic acid or methacrylic acid. .

The monomer unit (a1-1-1) which has a carboxy group may be comprised individually by 1 type, and may be comprised by 2 or more types.

(a1-1-2) Monomer unit having both ethylenically unsaturated groups and acid anhydride residues

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

As an acid anhydride, a well-known thing can be used, Specifically, Dibasic acid anhydrides, such as maleic anhydride, succinic anhydride, itaconic anhydride, a phthalic anhydride, tetrahydro phthalic anhydride, hexahydro phthalic anhydride, a chlorohydric anhydride; And acid anhydrides such as trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride and biphenyltetracarboxylic 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 an acid anhydride is from a developable viewpoint, Preferably it is 10-100 mol%, More preferably, it is 30-100 mol%.

(a1-1-3) Repeating unit derived from a monomer having a carboxyl group protected by an acid-decomposable group

The repeating unit derived from the monomer having a carboxyl group protected with an acid-decomposable group is preferably protected by an acid-decomposable group which the carboxyl groups described in the above (a1-1-1) and (a1-1-2) are described in detail below. Monomer unit having a residue.

As an acid-decomposable group, a well-known thing can be used as an acid-decomposable group in a positive resist for KrF and a positive resist for ArF so far, and is not specifically limited. Conventionally, as an acid-decomposable group, groups (e.g., acetal-based functional groups such as tetrahydropyranyl groups) which are relatively easy to decompose by an acid, and groups that are relatively hard to decompose by an acid (e.g., t-butyl ester group, t-butyl-based functional groups such as t-butyl carbonate groups) are known.

Among these acid-decomposable groups, the monomer unit having a residue in which the carboxyl group is protected by acetal or a residue in which the carboxyl group is protected by ketal is the basic physical properties of the resist, in particular, the sensitivity and pattern shape, the formation of contact holes, and the storage of the photosensitive resin composition. It is preferable from a stability point of view. Moreover, it is more preferable from a viewpoint of a sensitivity that a carboxy group is a residue protected by acetal or ketal represented by a following formula (a1-1) among acid-decomposable groups. Alternatively, if the carboxy group is the following formula (a1-1) or acetal Kane phthaloyl protection represented by the cup group, as a whole of the residue, - is a (C = O) of the structure ^{-O-CR 1 R 2 (OR} 3) have.

(In formula (a1-1), R <^1> and R <^2> represents a hydrogen atom or an alkyl group each independently, except when R <^1> and R <^2> are both hydrogen atoms. R <^3> represents an alkyl group. R ¹ or R ² and R ³ may be linked to form a cyclic ether.)

In formula (a1-1), R <^1> -R <^3> respectively independently represents a hydrogen atom or an alkyl group, and the alkyl group may be any of linear, branched, and cyclic. Here, both of R ¹ and R ² do not represent a hydrogen atom, and at least one of R ¹ and R ² represents an alkyl group.

In formula (a1-1), when R <^1> , R <^2> and R <^3> represent an alkyl group, the alkyl group may be linear, branched, or cyclic.

As a linear or branched alkyl group, it is preferable that it is C1-C12, It is more preferable that it is C1-C6, It is 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, t-butyl group, n-pentyl group, neopentyl group, n-hex A real group, a 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 a cyclic alkyl group, it is preferable that it is C3-C12, It is more preferable that it is C4-C8, It is more preferable that it is C4-C6. Examples of the cyclic alkyl group include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornyl group, isobornyl group and the like.

The said alkyl group may have a substituent and can illustrate a halogen atom, an aryl group, and an alkoxy group as a substituent. When R ¹ , R ² and R ³ are a haloalkyl group, and when they have an aryl group as a substituent, R ¹ , R ² and R ³ are an aralkyl group when they have a halogen atom as a substituent.

As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are 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 an 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, and a methoxy group or an ethoxy group is more preferable.

Moreover, when an 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 an alkyl group is a linear or branched alkyl group, it is carbon number as a substituent You may have a 3-12 cyclic alkyl group.

These substituents may further be substituted by the said substituent.

In formula (a1-1), R ¹ , R ² And when R <^3> represents an aryl group, it is preferable that the said aryl group is C6-C12, and it is more preferable that it is C6-C10. The said aryl group may have a substituent and can illustrate a C1-C6 alkyl group preferably as this substituent. As an aryl group, a phenyl group, tolyl group, cumenyl group, 1-naphthyl group etc. can be illustrated, for example.

In addition, R ¹ , R ² and R ³ may be bonded to each other to form a ring integrally with the carbon atom to which they are bonded. Examples of the ring structure when R ¹ and R ² , R ¹ and R ^3, or R ² and R ³ are bonded include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a tetrahydrofuranyl group, An adamantyl group, tetrahydropyranyl group, and the like.

In formula (a1-1), one of R ¹ and R ² 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 monomeric unit which has a residue represented by Formula (a1-1), and what synthesize | combined by a well-known method can also be used. For example, it can synthesize | combine by making (meth) acrylic acid react with vinyl ether in presence of an acidic catalyst, as shown below.

R ¹¹ represents a hydrogen atom or an alkyl group, and the alkyl group is the same as the alkyl group represented by R ¹ to R ³ in formula (a1-1). As R ¹¹ , a hydrogen atom or a methyl group is preferable.

R <^12> and R <^13> is -CH (R <^12> ) (R <^13> ), and is synonymous with R <^2> in Formula (a1-1), and R <^14> is synonymous with R <^1> in Formula (a). And R ¹⁵ are synonymous with R ³ in the formula (a1-1), and these are also in the same preferred range.

Said synthesis | combination may copolymerize (meth) acrylic acid previously with another monomer, and may make it react with vinyl ether in presence of an acidic catalyst after that.

As a monomer unit (a1-1) in this invention, the following are mentioned as a preferable example.

(In said formula, R <^1> represents a hydrogen atom or a C1-C4 alkyl group, respectively, L <^1> represents a carbonyl group or a phenylene group, and R <^2> represents a C1-C4 alkyl group, respectively. N1 and n2 are Each is an integer of 1 to 5, n3 is an integer of 1 to 4, and n4 is an integer of 1 to 3).

R ¹ each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom or a methyl group, and more preferably a methyl group.

L ¹ represents a carbonyl group or a phenylene group, and a carbonyl group is more preferable.

R <^2> respectively represents a hydrogen atom or a C1-C4 alkyl group, A hydrogen atom or a methyl group is preferable, and it is more preferable that all are hydrogen atoms.

As for n1, n2, n3, and n4, 0 is respectively preferable.

Among these, especially (1), (2), (5) or (7) is preferable, (2) or (7) is more preferable, and (7) is especially preferable.

As a preferable specific example of the repeating unit (a1-1) derived from the monomer which has a carboxyl group protected by the acid-decomposable group, the following monomeric unit can be illustrated. R represents a hydrogen atom or a methyl group.

(a1-2) Repeating unit derived from the monomer which has a phenolic hydroxyl group protected by the acid-decomposable group

(a1-2-1) Monomer unit having phenolic hydroxyl group

Examples of the monomer unit having a phenolic hydroxyl group include a hydroxystyrene-based monomer unit and a monomer unit in a novolak-based resin, but among these, the monomer unit derived from α-methylhydroxystyrene is a transparent viewpoint. Preferred at Among the monomer units having a phenolic hydroxyl group, the monomer units represented by the formula (a1-2) are preferable in view of transparency and sensitivity.

, R ²⁰ (wherein (a1-2) is a hydrogen atom or a methyl group, R ²¹ represents a single bond or a linking group, R ²² represents a halogen atom or an alkyl group, a is an integer of 1 ~ 5, b Represents an integer of 0 to 4, and a + b is 5 or less, and when R ²² is 2 or more, these R ²² may be mutually different or the same.)

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

In addition, R ²¹ 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, it is preferable. Examples of the divalent linking group for R ²¹ include an alkylene group, and specific examples in which R ²¹ is an alkylene group include a methylene group, an ethylene group, a propylene group, an isopropylene group, an n-butylene group, an isobutylene group, and a tert-butylene group. , Pentylene group, isopentylene group, neopentylene group, hexylene group and the like. Especially, it is preferable that R <^21> is a single bond, a methylene group, and an ethylene group. In addition, the said divalent coupling group may have a substituent, and a halogen atom, a hydroxyl group, an alkoxy group etc. are mentioned as a substituent.

In addition, although a shows the integer of 1-5, it is preferable that a is 1 or 2, and it is more preferable that a is 1 from a viewpoint of the effect of this invention or manufacture point.

Moreover, when the bond position of the hydroxyl group in a benzene ring makes the carbon atom couple | bonded with R <^{21> a} reference | standard (one position), it is preferable to couple | bond at four positions.

R ²² is a halogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms. Specifically, a fluorine atom, chlorine atom, bromine atom, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group and the like Can be mentioned. Especially, since manufacture is easy, it is preferable that they are a chlorine atom, a bromine atom, a methyl group, or an ethyl group.

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

Among the monomer units having a phenolic hydroxyl group, when R ²¹ is not an alkylene group in the formula (a1-2), the monomer unit represented by the formula (a1-2 ') is more preferable from the viewpoint of transparency and sensitivity. Do. As the linking group for R ²¹ , in addition to the alkylene group, an alkyleneoxycarbonyl group or the like (from the side of the main chain of the copolymer) can be preferably exemplified. In this case, the monomer unit having a phenolic hydroxyl group is It is preferable that it is represented by Formula (a1-2 ').

(Formula (a1-2 ') of, R ³⁰ is R ²⁰ and copper in the formula (a1-2), R ³² is R ²² and copper in the formula (a1-2), a and b are the formula ( It is synonymous with a and b in a1-2), and its preferable range is also the same.)

R <^33> represents a bivalent coupling group in a formula (a1-2 '), and can preferably illustrate an alkylene group. The alkylene group may be either linear or branched, and preferably has 2 to 6 carbon atoms, and is an ethylene group, a propylene group, an isopropylene group, an n-butylene group, a tert-butylene group, a pentylene group, or an isopentylene group. And a neopentylene group, a hexylene group, and the like. In addition, the divalent linking group may have a substituent, and a halogen atom, a hydroxyl group, an alkoxy group etc. are mentioned as a substituent. Among these, as R ³³ , an ethylene group, a propylene group, or a 2-hydroxypropylene group is preferable from the viewpoint of sensitivity.

(a1-2-2) Repeating unit derived from the monomer which has a phenolic hydroxyl group protected by the acid-decomposable group

The repeating unit derived from the monomer which has a phenolic hydroxyl group protected by the acid-decomposable group is a residue in which the phenolic hydroxyl group of the monomeric unit which has a (phenol) hydroxyl group is protected by the acid-decomposable group demonstrated in detail below. It is a monomer unit which has. As an acid-decomposable group, a well-known thing can be used as mentioned above, It does not specifically limit. Among the acid-decomposable groups, the monomer unit having a residue in which the phenolic hydroxyl group is protected by acetal or a residue in which the phenolic hydroxyl group is protected by ketal is the basic physical properties of the resist, in particular, the sensitivity and pattern shape, the storage stability of the photosensitive resin composition, It is preferable from a viewpoint of the formation of a contact hole. Moreover, it is more preferable from a viewpoint of a sensitivity that a phenolic hydroxyl group is a residue protected by the acetal or ketal represented by a formula (a1-1) among acid-decomposable groups. In the case where the phenolic hydroxyl group is a residue protected by acetal or ketal represented by the formula (a1-1), the entirety of the residue has a structure of -Ar-O-CR ¹ R ² (OR ³ ). Ar represents an arylene group.

Preferable examples of the acetal ester structure of the phenolic hydroxyl group include a combination of R ¹ = R ² = R ³ = methyl group and R ¹ = R ² = methyl group and R ³ = benzyl group.

Moreover, as a radically polymerizable monomer used in order to form the monomeric unit in which a phenolic hydroxyl group has the residue protected by acetal or ketal, the 1-alkoxyalkyl protecting body of hydroxy styrene, tetrahydropyra of hydroxy styrene, for example. Neyl protector, 1-alkoxyalkyl protector of α-methyl-hydroxystyrene, tetrahydropyranyl protector of α-methyl-hydroxystyrene, 1-alkoxyalkyl protector of 4-hydroxyphenylmethacrylate, Tetrahydropyranyl protector of 4-hydroxyphenyl methacrylate, 1-alkoxyalkyl protector of 4-hydroxybenzoic acid (1-methacryloyloxymethyl) ester, 4-hydroxybenzoic acid (1-methacryl) Tetrahydropyranyl protector of loyloxymethyl) ester, 1-alkoxyalkyl protector of 4-hydroxybenzoic acid (2-methacryloyloxyethyl) ester, 4-hydroxybenzoic acid (2-methacryloyl) Oxyethyl) ester Lahydropyranyl protector, 1-alkoxyalkyl protector of 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester, tetrahydro of 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester Pyranyl protecting agent, 1-alkoxyalkyl protecting agent of 4-hydroxybenzoic acid (3-methacryloyloxy-2-hydroxypropyl) ester, 4-hydroxybenzoic acid (3-methacryloyloxy-2- Tetrahydropyranyl protecting body of hydroxypropyl) ester, etc. are mentioned.

Among these, 1-alkoxyalkyl protecting group of 4-hydroxyphenyl methacrylate, tetrahydropyranyl protecting group of 4-hydroxyphenyl methacrylate, 4-hydroxybenzoic acid (1-methacryloyloxymethyl) Of 1-alkoxyalkyl protector of ester, tetrahydropyranyl protector of 4-hydroxybenzoic acid (1-methacryloyloxymethyl) ester, and 4-hydroxybenzoic acid (2-methacryloyloxyethyl) ester 1-alkoxyalkyl protector, tetrahydropyranyl protector of 4-hydroxybenzoic acid (2-methacryloyloxyethyl) ester, 1- of 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester Alkoxyalkyl protector, tetrahydropyranyl protector of 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester, 4-hydroxybenzoic acid (3-methacryloyloxy-2-hydroxypropyl) ester 1-alkoxyalkyl protecting group, 4-hydroxybenzoic acid (3-methacryloyloxy-2-hydroxy The tetrahydropyranyl protecting body of the hydroxypropyl) ester is preferable from the viewpoint of transparency.

As a specific example of the acetal protecting group and ketal 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-benzyloxyethyl group, etc. can be mentioned, These can be used individually or in combination of 2 or more types.

A commercially available radical may be used for the radically polymerizable monomer used for forming a monomeric unit (a1), and what synthesize | combined by a well-known method can also be used. 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.

As a preferable specific example of a monomer unit (a1-2), the following monomer unit can be illustrated.

From the viewpoint of the sensitivity, the content rate of a monomeric unit (a1) among the monomeric units which comprise (A) component has preferable 3-70 mol% of copolymers of (A) component as a whole, and 5-60 mol% Is more preferable, and 10-50 mol% is more preferable.

The repeating unit derived from the monomer which has a carboxyl group protected by an acid-decomposable group has the characteristics that image development is quick compared with the repeating unit derived from the monomer which has a phenolic hydroxyl group protected by the acid-decomposable group. Therefore, when it is desired to develop rapidly, repeating units derived from a monomer having a carboxyl group protected by an acid-decomposable group are preferable. Conversely, when it is desired to slow development, it is preferable to use repeating units derived from a monomer having a phenolic hydroxyl group protected with an acid-decomposable group.

(a2) Monomer unit having a crosslinking group

The component (A) has a monomer unit (a2) having a crosslinking group. The crosslinking group is not particularly limited as long as it is a group causing a curing reaction by heat treatment. As an aspect of the monomer unit which has a preferable crosslinking group, the monomer unit containing at least 1 chosen from the group which consists of a cyclic ether residue of a 3-membered ring and / or a 4-membered ring, and an ethylenically unsaturated group is mentioned. In more detail, the following are mentioned.

(a2-1) Monomer unit having cyclic ether residues of three- and / or four-membered rings

It is preferable that the said (A) copolymer contains the monomeric unit (monomer unit (a2-1)) which has a 3 membered ring and / or a 4 membered cyclic ether residue. The 3-membered ring cyclic ether residue is also called an epoxy group, and the 4-membered ring cyclic ether residue is also called an oxetanyl group. As a monomer unit (a2-1) which has the said epoxy group and / or oxetanyl group, it is preferable that it is a monomer unit which has an alicyclic epoxy group and / or oxetanyl group, and it is more preferable that it is a monomer unit which has an oxetanyl group.

The monomer unit which has an epoxy group and / or an oxetanyl group should just have at least one epoxy group or oxetanyl group in one monomer unit, One or more epoxy groups, one or more oxetanyl groups, two or more epoxy groups, or Although it may have two or more oxetanyl groups, it is not specifically limited, It is preferable to have 1-3 epoxy groups and / or oxetanyl groups in total, It is more preferable to have 1 or 2 epoxy groups and / or oxetanyl groups in total. It is preferable, and it is 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 monomer unit which has an epoxy group, For example, glycidyl acrylate, glycidyl methacrylate, the glycidyl (alpha)-ethyl acrylate, the glycine (alpha)-n-propyl acrylate Dill, α-n-butyl acrylate glycidyl, acrylic acid-3,4-epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxy Heptyl, α-ethylacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, paragraph of Japanese Patent No. 4168443 The compound containing the alicyclic epoxy skeleton of 0031-0035, etc. are mentioned.

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

As a specific example of the radically polymerizable monomer used in order to form the monomer unit which has an epoxy group and / or an oxetanyl group, it is preferable that it is a monomer containing a methacrylic acid ester structure, and a monomer containing an acrylate ester structure.

Among these monomers, more preferably, a compound containing an alicyclic epoxy skeleton described in paragraphs 0034 to 0035 of Japanese Patent No. 4168443 and oxetanyl described in paragraphs 0011 to 0016 of Japanese Patent Application Laid-Open No. 2001-330953. It is (meth) acrylic acid ester which has a group, Especially preferably, it is (meth) acrylic acid ester which has the oxetanyl group of Paragraph 0011 of Unexamined-Japanese-Patent No. 2001-330953-0016. Among these, preferred are 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, acrylic acid (3-ethyloxetan-3-yl) methyl, and methacrylic acid (3-ethyl jade). Cetane-3-yl) methyl, most preferred are acrylic acid (3-ethyloxetan-3-yl) methyl, and methacrylic acid (3-ethyloxetan-3-yl) methyl. These monomer units can be used individually by 1 type or in combination of 2 or more types.

It is preferable that a monomer unit (a2-1) has the residue selected from the group which consists of following formula (a2-1-1) and formula (a2-1-2).

The monomer unit (a2-1) having any of the three residues represented by the formula (a2-1-1) is one or more hydrogen atoms from the structure represented by the formula (a2-1-1). It means having a group except.

It is more preferable that the monomer unit (a2-1) has a 3,4-epoxycyclohexyl group, a 2,3-epoxycyclohexyl group, and a 2,3-epoxycyclopentyl group.

(In Formula (a2-1-2), R ^1b and R ^6b each independently represent a hydrogen atom or an alkyl group, and R ^2b , R ^3b , R ^4b , R ^5b , R ^7b , R ^8b , R ^9b , R ^10b Each independently represents a hydrogen atom, a halogen atom, an alkyl group, or an aryl group.)

In formula (a2-1-2), R ^1b and R ^6b each independently represent a hydrogen atom or an alkyl group, preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and a hydrogen atom or an alkyl group having 1 to 5 carbon atoms ( Hereinafter, it is more preferable that it is also called "lower alkyl group."

R ^2b , R ^3b , R ^4b , R ^5b , R ^7b , R ^8b , R ^9b , and R ^10b each independently represent a hydrogen atom, a halogen atom, an alkyl group, or an aryl group.

As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom can be illustrated, A fluorine atom and a chlorine atom are more preferable, A fluorine atom is more preferable.

The alkyl group may be any of linear, branched, and cyclic, or may have a substituent. As a linear and branched alkyl group, it is preferable that it is C1-C8, It is more preferable that it is C1-C6, It is more preferable that it is C1-C4. As a cyclic alkyl group, it is preferable that it is C3-C10, It is more preferable that it is C4-C8, It is more preferable that it is C5-C7. In addition, the linear and branched alkyl groups may be substituted with cyclic alkyl groups, and the cyclic alkyl groups may be substituted with linear and / or branched alkyl groups.

As an aryl group, it is preferable that it is a C6-C20 aryl group, and it is more preferable that it is a C6-C10 aryl group.

The said alkyl group and the aryl group may further have a substituent, As a substituent which the alkyl group may have, a halogen atom and an aryl group can be illustrated, As a substituent which an aryl group may have, a halogen atom and an alkyl group can be illustrated.

Among these, R ^2b , R ^3b , R ^4b , R ^5b , R ^7b , R ^8b , R ^9b , and R ^10b each independently represent a hydrogen atom, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group, or one having 1 to 4 carbon atoms. It is more preferable that it is a perfluoroalkyl group of 4.

As group which has a residue represented by said formula (a2-1-2), a (3-ethyloxetan-3-yl) methyl group can be illustrated preferably.

As a preferable specific example of monomer unit (a2-1), the following monomer unit can be illustrated. R represents a hydrogen atom or a methyl group.

In the present invention, an oxetanyl group is preferred among the three- and four-membered cyclic ether residues from the viewpoint of curing sensitivity. Moreover, in this invention, an alicyclic epoxy group and an oxetanyl group are preferable from a viewpoint of a transmittance | permeability (transparency). As mentioned above, in this invention, as a 3 and 4 membered cyclic ether residue, an alicyclic epoxy group and an oxetanyl group are preferable, and an oxetanyl group is especially preferable.

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

Copolymer used in the present invention, -NH-CH ₂ -OR is also preferred structural units (a2-2) having a group represented by (R is an alkyl group having 1 to 20 carbon atoms). By having a structural unit (a2-2), hardening reaction can be raise | generated by loose | gentle heat processing, and the cured film excellent in the agent characteristic can be obtained. Here, 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), More preferably, it is a structural unit which has group represented by the following general formula (a2-20).

General formula (a2-20)

(In general formula (a2-20), 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, 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.

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.

(a2-3) Monomer unit having an ethylenically unsaturated group

As one of the monomer units (a2) which have a crosslinking group, the monomer unit (a2-3) which has an ethylenically unsaturated group is mentioned (henceforth "monomer unit (a2-3)"). As a monomer unit (a2-3) which has the said ethylenically unsaturated group, the monomer unit which has an ethylenically unsaturated group in a side chain is preferable, The monomer unit which has an ethylenically unsaturated group at the terminal and has a C3-C16 side chain is more preferable. And the monomer unit which has a side chain represented by a formula (a2-3-1) is more preferable.

(In formula (a2-3-1), R <^1> represents a C1-C13 bivalent coupling group and R <^3> represents a hydrogen atom or a methyl group.)

R <^1> is a C1-C13 bivalent coupling group, contains an alkenyl group, an arylene group, or group which combined these, and may contain bonds, such as an ester bond, an ether bond, an amide bond, and a urethane bond. The alkenyl group may be a cyclic alkenyl group. In addition, the divalent linking group may have substituents, such as a hydroxyl group and a carboxy group, in arbitrary positions. As a specific example of R <^1>, the bivalent coupling group represented by Formula (A-1)-a formula (A-10) is mentioned.

Among the side chains represented by formula (a2-3-1), aliphatic side chains are preferable. Among the side chains having a linking group represented by formula (a2-3-1), a side chain whose terminal is an acryloyl group or a methacryloyl group is more preferable.

Moreover, it is preferable that 1 mol of ethylenically unsaturated groups contained in the side chain represented by said formula (a2-3-1) are contained with respect to 150-2,000 g of said (A) polymer, and it is 1 mol with respect to 200-1,300 g. It is more preferable to contain.

Although the method of obtaining the monomer unit (a2-3) which has a side chain represented by a formula (a2-3-1) is not specifically limited, For example, the polymer which has a specific functional group is previously mentioned by superposition | polymerization methods, such as radical polymerization. It can be set as the copolymer which has a monomeric unit (a2-3) by making and reacting the compound which has an ethylenically unsaturated group to the group and terminal which react with this specific functional group (henceforth a specific compound).

Here, as said specific functional group, a carboxy group, an epoxy group, a hydroxyl group, the amino group which has active hydrogen, a phenolic hydroxyl group, an isocyanate group, etc. are mentioned. The monomer which has a specific functional group for synthesize | combining the polymer which has a specific functional group is mentioned later.

As a combination of the group which reacts with the specific functional group and the specific functional group which the said specific compound has, the combination of a carboxy group and an epoxy group, the combination of a carboxy group and an oxetanyl group, the combination of a hydroxy group and an isocyanate group, the combination of a phenolic hydroxyl group and an epoxy group, the carboxy group and A combination of an isocyanate group, a combination of an amino group and an isocyanate group, a combination of a hydroxy group and an acid chloride, and the like.

Moreover, as said specific compound, glycidyl methacrylate, glycidyl acrylate, 3, 4- epoxycyclohexyl methyl methacrylate, 3, 4- epoxy cyclohexyl methyl acrylate, isocyanate ethyl methacrylate, isocyanate Ethyl acrylate, methacrylic acid chloride, a chloric acid chloride, methacrylic acid, acrylic acid etc. are mentioned.

As a preferable specific functional group and specific compound combination, the combination of the carboxy group which is a specific functional group, the glycidyl methacrylate which is a specific compound, and the combination of the hydroxyl group which is a specific functional group and the isocyanate ethyl methacrylate which are a specific compound are mentioned.

In the present invention, the monomer unit (a2-3) is preferably a monomer unit represented by formula (a2-3-2).

(Formula (a2-3-2) of, R ¹ and R ¹ are the same also accept a preferable range in the formula ^{(a2-3-1). R 2, R} 3 are, each independently, a hydrogen atom or a methyl group, respectively .)

Although the specific example of the monomer which has a specific functional group necessary for obtaining the polymer which has a specific functional group is given to the following, it is not limited to these.

Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, mono (2- (acryloyloxy) ethyl) phthalate, mono (2- (methacryloyloxy) ethyl) phthalate, and N- ( Carboxyphenyl) maleimide, N- (carboxyphenyl) methacrylamide, N- (carboxyphenyl) acrylamide, etc. are mentioned.

As a monomer which has an epoxy group, glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, 3-ethenyl-7-oxabicyclo [4.1.0] heptane, 1, 2- epoxy, for example -5-hexene, 1,7-oxadiene monoepoxide, 3, 4- epoxycyclohexyl methyl methacrylate, 3, 4- epoxycyclohexyl methyl acrylate, etc. are mentioned.

As a monomer which has a hydroxy group, for example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate , 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, caprolactone 2- (acryloyloxy) ethyl ester, caprolactone 2- (methacryloyloxy) ethyl ester, poly (ethylene glycol) ethyl ether acrylate, poly (ethylene glycol) ethyl ether methacrylate, 5-acrylo Yloxy-6-hydroxynorbornene-2-carboxylic-6-lactone, 5-methacryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone, etc. are mentioned. have.

As a monomer which has an amino group which has active hydrogen, 2-aminoethyl acrylate, 2-aminomethyl methacrylate, etc. are mentioned.

As a monomer which has a phenolic hydroxyl group, hydroxy styrene, N- (hydroxyphenyl) acrylamide, N- (hydroxyphenyl) methacrylamide, N- (hydroxyphenyl) maleimide, etc. are mentioned, for example. .

Moreover, as a monomer which has an isocyanate group, acryloyl ethyl isocyanate, methacryloyl ethyl isocyanate, m- tetramethyl xylene isocyanate, etc. are mentioned, for example.

In addition, in this invention, when obtaining the polymer which has a specific functional group, the repeating unit derived from the monomer which has the monomer which has the specific functional group mentioned above, and the carboxyl group protected by the acid-decomposable group (a1), or the phenolic group protected by the acid-decomposable group The monomer used as the repeating unit derived from the monomer which has a hydroxyl group is used together. Moreover, the monomer used as another monomer unit (a3) other than (a1) and (a2) mentioned later can be used together.

Although the method of obtaining the polymer which has a specific functional group used for this invention is not specifically limited, For example, in the solvent which coexisted the monomer which has a specific functional group, another monomer, and a polymerization initiator etc. as needed, it is 50-110 degreeC. It can obtain by polymerizing under temperature. In that case, if the solvent used melt | dissolves the monomer which comprises the polymer which has a specific functional group, and the polymer which has a specific functional group, it will not specifically limit. As a specific example, the solvent described in the (C) solvent mentioned later is mentioned. The polymer which has a specific functional group obtained in this way is a state of the solution melt | dissolved in the solvent normally.

Then, the polymer and specific compound which have obtained the specific functional group are made to react, and the monomer unit (a2-3) which has an ethylenically unsaturated group in the terminal of a side chain can be obtained. In that case, normally, the solution of the polymer which has a specific functional group is provided to reaction. For example, the monomer unit (a2-3) is made by reacting glycidyl methacrylate at the temperature of 80 to 150 degreeC in the presence of catalysts, such as benzyl triethylammonium chloride, to the solution of the acrylic polymer which has a carboxyl group. You can get it.

In addition, in order to form a monomer unit (a2-3), in addition to using the above-mentioned polymer reaction, aryl methacrylate, allyl acrylate, etc. may be used as a radically polymerizable monomer. These monomer units can be used individually or in combination of 2 or more types.

In this invention, it is preferable to contain a monomeric unit (a2-1) as a monomeric unit (a2).

From the viewpoint of the various tolerances and transparency of the formed film, 5-60 mol% is preferable, as for content of a monomer unit (a2), in the monomeric unit which comprises (A) component, 10-55 mol% is more preferable, 20 50 mol% is more preferable. If it is in the range of said numerical value, transparency of a cured film obtained from the photosensitive resin composition and ITO sputter resistance will become favorable.

<<< preferred aspect of structural unit (a2) >>>

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

When the polymer containing the said structural unit (a2) contains the said structural unit (a1), a mono structural unit (a2) is a chemical | medical agent in the polymer containing the said structural unit (a1) and a structural unit (a2). 3-70 mol% is preferable from a viewpoint of tolerance, and 10-60 mol% is more preferable.

In this invention, in addition to which aspect, it is preferable to contain 3-70 mol% of structural units (a2) among all the structural units of (A) component, and to contain 10-60 mol% more. desirable.

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

(a3) other monomer units

In the present invention, the component (A) may have other monomer units (a3) except for the monomer units (a1) and (a2). As a monomer used as another monomer unit (a3), styrene, (meth) acrylic-acid alkylester, (meth) acrylic-acid cyclic alkylester, (meth) acrylic-acid aryl ester, unsaturated dicarboxylic acid diester, and a bicyclo unsaturated compound, for example Logistics, maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated dicarboxylic anhydrides, and other unsaturated compounds.

Specifically, styrene, tert-butoxy styrene, methyl styrene, hydroxy styrene, (alpha) -methyl styrene, acetoxy styrene, methoxy styrene, ethoxy styrene, chloro styrene, methyl vinyl benzoate, ethyl vinyl benzoate, (meth) Acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, tert-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth) Structural units by 2-hydroxypropyl acrylate, benzyl (meth) acrylic acid, isobornyl (meth) acrylate, glycidyl methacrylate, acrylonitrile, etc. are mentioned. In addition, Paragraph 0021 of Unexamined-Japanese-Patent No. 2004-264623-the compound of 0024 can be mentioned. Especially, the group in which the group which reacts with a monomeric unit (a2) and a separately added crosslinking agent by (final) heat processing generate | occur | produce is preferable from a viewpoint of a film strength. Specifically, (meth) acrylic acid tertiary alkyl ester is preferable, and (meth) acrylic acid tert-butyl is more preferable. The monomer used as a monomer unit (a3) can be used individually or in combination of 2 or more types.

Moreover, it is preferable from the point of a sensitivity that (A) copolymer contains 1-15 mol% of monomer units which have an unprotected carboxyl group, or a monomer unit which has an unprotected phenolic hydroxyl group.

The molecular weight of the (A) copolymer is preferably in the range of 1,000 to 200,000, and more preferably in the range of 2,000 to 50,000, based on the polystyrene reduced weight average molecular weight. If it is in the range of said numerical value, a sensitivity and ITO sputter tolerance are more favorable.

It is preferable that the photosensitive resin composition of this invention contains the (A) copolymer component in the ratio of 80 weight% or more. The copolymer (A) may contain only one type or may contain two or more types. In this invention, two or more types are preferable. By setting it as two or more types, there exists a tendency for solvent resistance to improve more.

Moreover, although various methods are known also about the synthesis | combining method of (A) component, For example, radical polymerization containing the radically polymerizable monomer used in order to form the monomeric unit represented by the said (a1) and said (a2) at least. The monomer mixture can be synthesized by polymerizing with a radical polymerization initiator in an organic solvent.

(B) photoacid generator

In this invention, the oxime sulfonate compound represented by a following formula (b1) is contained. In the present invention, as the solvent, a solvent having a boiling point of less than 180 ° C and a solvent having a boiling point of 180 ° C or more, and an oxime sulfonate are used, have high sensitivity, excellent chemical resistance, and storage stability. It is possible to provide an excellent photosensitive composition.

(In General Formula (b1), R ⁵ represents an alkyl group or an aryl group.)

As an alkyl group of R <^5> , a C1-C10 linear or branched alkyl group is preferable. The alkyl group of R ⁵ is an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cyclic alicyclic group such as a cyclic alkyl group (7,7-dimethyl-2-oxonorbornyl group). Containing, preferably a bicycloalkyl group).

As an aryl group of R <^5> , a C6-C11 aryl group is preferable and a phenyl group or a naphthyl group is more preferable. The aryl group of R ⁵ may be substituted with a lower alkyl group, an alkoxy group or a halogen atom.

As an oxime sulfonate compound represented by said formula (b1), it is preferable that it is an oxime sulfonate compound represented by a formula (OS-3), a formula (OS-4), or a formula (OS-5).

(In formula (OS-3)-Formula (OS-5), R <^1> represents an alkyl group, an aryl group, or a heteroaryl group, R <^2> respectively independently represents a hydrogen atom, an alkyl group, an aryl group, or a halogen atom, and R ⁶ are, each independently, a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group and represents an amino-sulfonyl group, or an alkoxy-sulfonyl, X is O or S, n represents 1 or 2, m is 0 to 6 Represents an integer.)

In said formula (OS-3)-(OS-5), the alkyl group, aryl group, or heteroaryl group in R <^1> may have a substituent.

As said alkyl group in R <^1> , it is preferable that it is the C1-C30 alkyl group which may have a substituent in said Formula (OS-3)-(OS-5).

Examples of the substituent which the alkyl group in 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.

As an alkyl group in R <^1> , a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-octyl group , n-decyl group, n-dodecyl group, trifluoromethyl group, perfluoropropyl group, perfluorohexyl group, benzyl group, phenoxyethyl group, methylthioethyl group, phenylthioethyl group, ethoxycarbonylethyl group, phenoxy Cycarbonylethyl group and the dimethylaminocarbonylethyl group are mentioned.

Among these, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-de The preferred group, n-dodecyl group, trifluoromethyl group, perfluoropropyl group, perfluorohexyl group, and benzyl group are preferable.

Moreover, as said aryl group in R <^1> , the aryl group of 6-30 total carbons which may have a substituent is preferable in said Formula (OS-3)-(OS-5).

Examples of the substituent that the aryl group in R ¹ may have include a halogen atom, an alkyl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an aminocarbonyl group, a sulfonic acid group and an aminosulfonyl group. And an alkoxysulfonyl group.

As an aryl group in R <^1> , a phenyl group, p-methylphenyl group, p-chlorophenyl group, pentachlorophenyl group, pentafluorophenyl group, o-methoxyphenyl group, p-phenoxyphenyl group, p-methylthiophenyl group, p-phenyl A thiophenyl group, p-ethoxycarbonylphenyl group, p-phenoxycarbonylphenyl group, and p-dimethylaminocarbonylphenyl group are mentioned.

Among these, a phenyl group, p-methylphenyl group, p-chlorophenyl group, pentachlorophenyl group, pentafluorophenyl group, o-methoxyphenyl group, and p-phenoxyphenyl group are preferable.

In addition, as said heteroaryl group in R <^1> , the heteroaryl group of 4-30 total carbons which may have a substituent is preferable in said Formula (OS-3)-(OS-5).

Examples of the substituent that the heteroaryl group in R ¹ may have include a halogen atom, an alkyl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an aminocarbonyl group, a sulfonic acid group, and an aminosulfo. A silyl group and an alkoxysulfonyl group are mentioned.

In the formulas (OS-3) to (OS-5), at least one ring may be a heteroaromatic ring in the heteroaryl group in R ¹ , and a heteroaromatic ring and a benzene ring may be condensed, for example.

As a heteroaryl group in R ^1, in the group consisting of a thiophene ring, a pyrrole ring, a thiazole ring, an imidazole ring, a furan ring, a benzothiophene ring, a benzothiazole ring, and a benzoimidazole ring, which may have a substituent. The group remove | excluding one hydrogen atom from the selected ring is mentioned.

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.

In Formulas (OS-3) to (OS-5), one or two of R ² present in the compound is preferably 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 that it is an atom, It is especially preferable that one is an alkyl group and the remainder is a hydrogen atom.

In said formula (OS-3)-(OS-5), the alkyl group or aryl group in R <^2> may have a substituent.

As a substituent which the alkyl group or aryl group in 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 an alkyl group in R <^2> , it is preferable that it is a C1-C12 alkyl group which may have a substituent, and it is more preferable that it is a C1-C6 alkyl group which may have a substituent.

Specifically as an alkyl group in R <^2> , a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, allyl group, n-pen Methyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, perfluorohexyl, chloromethyl, bromomethyl, methoxymethyl, benzyl, phenoxyethyl, methylthioethyl, A phenylthio ethyl group, an ethoxy carbonyl ethyl group, a phenoxy carbonyl ethyl group, and a dimethylamino carbonyl ethyl group are mentioned.

Among these, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, n-hexyl group, allyl group, chloromethyl group, bromomethyl group, methoxymethyl group , Benzyl group is preferable, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, n-hexyl group is more preferable, and methyl group, ethyl group, n- A propyl group, n-butyl group, n-hexyl group is more preferable, and a methyl group is especially preferable.

As an aryl group in R <^2> , it is preferable that it is a C6-C30 aryl group which may have a substituent.

Specifically as an aryl group in R <^2> , a phenyl group, p-methylphenyl group, o-chlorophenyl group, p-chlorophenyl group, o-methoxyphenyl group, p-phenoxyphenyl group, p-methylthiophenyl group, p-phenylthio A phenyl group, p-ethoxycarbonylphenyl group, p-phenoxycarbonylphenyl group, and p-dimethylaminocarbonylphenyl group are mentioned.

Among these, a phenyl group, p-methylphenyl group, o-chlorophenyl group, p-chlorophenyl group, o-methoxyphenyl group, and p-phenoxyphenyl group are preferable.

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

Among these, a chlorine atom and a bromine atom are preferable.

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

In 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 2 desirable.

In said formula (OS-3)-(OS-5), the alkyl group and alkyloxy group in R <^6> may have a substituent.

In said formula (OS-3)-(OS-5), as an alkyl group in R <^6> , it is preferable that it is a C1-C30 alkyl group which may have a substituent.

Examples of the substituent which the alkyl group in 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.

As an alkyl group in R <^6> , a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-octyl group , n-decyl group, n-dodecyl group, trifluoromethyl group, perfluoropropyl group, perfluorohexyl group, benzyl group, phenoxyethyl group, methylthioethyl group, phenylthioethyl group, ethoxycarbonylethyl group, phenoxy Cycarbonylethyl group and the dimethylaminocarbonylethyl group are mentioned.

Among these, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-de The preferred group, n-dodecyl group, trifluoromethyl group, perfluoropropyl group, perfluorohexyl group, and benzyl group are preferable.

In said formula (OS-3)-(OS-5), as an alkyloxy group in R <^6> , it is preferable that it is a C1-C30 alkyloxy group which may have a substituent.

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

Examples of the alkyloxy group in R ⁶ include methyloxy group, ethyloxy group, butyloxy group, hexyloxy group, phenoxyethyloxy group, trichloromethyloxy group, ethoxyethyloxy group, methylthioethyloxy group and phenyl Thioethyloxy group, ethoxycarbonylethyloxy group, phenoxycarbonylethyloxy group, and dimethylaminocarbonylethyloxy group.

Among these, methyloxy group, ethyloxy group, butyloxy group, hexyloxy group, phenoxyethyloxy group, trichloromethyloxy group, or ethoxyethyloxy group is preferable.

As said aminosulfonyl group in R <^6> , said methylaminosulfonyl group, the dimethylaminosulfonyl group, the phenylaminosulfonyl group, the methylphenylaminosulfonyl group, and aminosulfonyl group in said Formula (OS-3)-(OS-5) are mentioned. have.

As said alkoxysulfonyl group in R <^6> , said methoxy sulfonyl group, an ethoxy sulfonyl group, a propyl ox sulfonyl group, and a butyl ox sulphonyl group are mentioned in said Formula (OS-3)-(OS-5).

Moreover, in said formula (OS-3)-(OS-5), m shows 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 Do.

Moreover, it is especially preferable that the compound containing the oxime sulfonate compound represented by said Formula (b1) is an oxime sulfonate compound represented by either of following formula (OS-6)-(OS-11).

(In formula (OS-6)-(OS-11), R <^1> represents an alkyl group, an aryl group, or a heteroaryl group, R <^7> represents a hydrogen atom or a bromine atom, R <^8> is a hydrogen atom, C1-C8 An 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 Indicates.)

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

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

R ⁸ in formulas (OS-6) to (OS-11) is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or a chlorophenyl group It is preferable to represent 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 more preferable that it is a C1-C6 alkyl group, It is especially preferable that it is a methyl group.

R <^9> in formula (OS-8) and (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 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, any one or a mixture may be sufficient about the three-dimensional 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)-a formula (OS-5), this invention is not limited to these.

It is preferable that it is a compound represented by a formula (OS-1) as said compound containing the oxime sulfonate compound represented by a formula (b1).

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

X represents —O—, —S—, —NH—, —NR ⁵ —, —CH ₂ —, —CR ⁶ H—, or —CR ⁶ R ⁷ —, and R ⁵ to R ⁷ represent an alkyl group, or And an aryl group.

R ²¹ to R ²⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amide group, a sulfo group, a cyano group, or an aryl group. Two of R ²¹ to R ²⁴ may be bonded to each other to form a ring.

As R <^21> -R <^24> , a hydrogen atom, a halogen atom, and an alkyl group are preferable, Moreover, the aspect which at least two of R <^21> -R <^24> couple | bonds with each other and forms an aryl group is also mentioned preferably. Especially, the sun whose R <^21> -R <^{24> is} all hydrogen atoms is preferable from a viewpoint of a sensitivity.

All the functional groups described may further have a substituent.

It is preferable that the compound represented by said formula (OS-1) is a compound represented by a following formula (OS-2).

In said formula (OS-2), R <^1> , R <^2> , R <^21> -R <^24> is synonymous with the thing in Formula (OS-1), respectively, and a preferable example is also the same.

Among these, the aspect whose R <^1> in a formula (OS-1) and a formula (OS-2) is a cyano group or an aryl group is more preferable, is represented by a formula (OS-2), R <^1> is a cyano group, Most preferred is a phenyl group or a naphthyl group.

In addition, in the said oxime sulfonate compound, about either the stereo structure (E, Z etc.) of an oxime and a benzothiazole ring, respectively, any may be sufficient as it, or a mixture may be sufficient as it.

Although the specific example (example compound b-1-b-34) of the compound represented by the formula (OS-1) which can be used suitably for this invention below is shown, this invention is not limited to this. In addition, Me represents a methyl group, Et represents an ethyl group, Bn represents a benzyl group, Ph represents a phenyl group.

Among the above-mentioned compounds, b-9, b-16, b-31, and b-33 are preferable from the viewpoint of both sensitivity and stability.

It is preferable that the said compound containing the oxime sulfonate compound represented by Formula (b1) is also an oxime sulfonate compound represented by following formula (b2).

(In formula (b2), R <^5> represents an alkyl group or an aryl group, X represents an alkyl group, an alkoxy group, or a halogen atom, m represents the integer of 0-3, when m is 2 or 3, X may be same or different.)

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

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

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

m is preferably 0 or 1.

In formula (b2), m is 1, X is a methyl group, a substitution position of X is an ortho position, R <^5> is a C1-C10 linear alkyl group, and 7- 7- dimethyl- 2-oxonorbornylmethyl group Or a compound that is a p-toluyl group is particularly preferred.

It is preferable that the compound containing the oxime sulfonate compound represented by Formula (b1) is also an oxime sulfonate compound represented by Formula (b3).

(In formula, R ^B1 represents an alkyl group, an alkoxy group, or a halogen atom, and R ^B2 represents an alkyl group or an aryl group.)

R ^B1 is preferably an alkoxy group, preferably an alkoxy group having 1 to 5 carbon atoms, and more preferably a methoxy group.

As R ^B2 , an alkyl group is preferable, and a methyl group, an ethyl group, n-propyl group, n-butyl group, n-octyl group, trifluoromethyl group, pentafluoroethyl group, perfluoro-n-propyl group, and perfluoro -n-butyl group, p-tolyl group, 4-chlorophenyl group or pentafluorophenyl group is preferable.

As a specific example of a preferable oxime sulfonate compound, the following compound (i)-(v) etc. are mentioned, It can be used individually by 1 type, or can use two or more types together. Compound (i)-(v) can be obtained as a commercial item. Moreover, it can also be used in combination with another kind of (B) photo-acid generator.

In the photosensitive resin composition of this invention, (B) oxime sulfonate compound is 0.1-100 mass parts with respect to all the resin components (preferably solid content, more preferably said (A) copolymer) in the photosensitive resin composition. It is preferable to use 10 mass parts, and it is more preferable to use 0.5-10 mass parts.

(C) solvent

In this invention, at least 1 type of boiling point contains a solvent below 180 degreeC, and at least 1 type of boiling point contains a 180 degreeC or more solvent. And (the total amount of the solvent whose boiling point is less than 180 ° C): (the total amount of the solvent having a boiling point of 180 ° C or more) is 99: 1 to 50:50 in terms of mass, preferably 99: 1 to 70:30, and more preferably Is contained in a ratio of 99: 1 to 90:10, most preferably 99: 1 to 95: 5.

In particular, by setting the (total amount of the solvent having a boiling point of less than 180 ° C): (the total amount of the solvent having a boiling point of 180 ° C or more) in the range of 99: 1 to 90:10, the effect of not impairing the applicability of the photosensitive resin composition can be obtained. have.

By using two or more such solvents and employing a compound containing an oxime sulfonate residue represented by the general formula (b1) as a photoacid generator, any of sensitivity, storage stability, solvent resistance, and exposure margin An excellent photosensitive resin composition can be obtained. In particular, in combination with a photoacid generator, the effect was very unexpected.

(Solvent with boiling point below 180 ° C)

It is preferable that the boiling point in this invention is 120-179 degreeC of the solvent whose boiling point is less than 180 degreeC, It is more preferable that it is 130-178 degreeC, It is still more preferable that it is 140-178 degreeC.

One type or two or more types of solvents whose boiling point in this invention is less than 180 degreeC may be sufficient as them. In the case of two or more types, the boiling point of each component should just be less than 180 degreeC.

As the solvent having a boiling point of less than 180 ° C, a known solvent can be used. Specifically, 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 As glycol monoalkyl ether acetates, esters, ketones, amides, lactones, etc., a thing with a boiling point below 180 degreeC can be employ | adopted widely.

Preferably, they are propylene glycol monomethyl ether acetate (PGMEA), diethylene glycol ethyl methyl ether (hysorb EDM), and ethyl 3-ethoxypropionate.

It is preferable that distribution coefficient LogP is -0.5-1.0, and, as for the solvent whose boiling point is less than 180 degreeC, it is more preferable that it is -0.3-0.8. By setting it as such a range, compatibility with a polymer becomes more favorable and there exists a tendency for ITO sputter resistance to improve more.

In this specification, the partition coefficient LogP denotes an octanol-water partition coefficient. The measurement of octanol-water partition coefficient (LogP value) can be generally performed by the flask penetration method described in JIS JP Z7260-107 (2000). In addition, the octanol-water partition coefficient (LogP value) may be estimated by calculation chemical method or empirical method instead of actual measurement. As a calculation method, Crippen's fragmentation method (J. Chem. Inf. Comput. Sci., 27, 21 (1987)), Viswanadhan's fragmentation method (J. Chem. Inf. Comput. Sci., 29, 163 (1989)), Broto's fragmentation method (Eur. J. Med. Chem.-Chim. Theor., 19, 71 (1984)) and the like are known. In the present invention, the Crippen's fragmentation method (J. Chem. Inf. Comput. Sci., 27, 21 (1987)) is used.

The CLogP value is a value obtained by calculating the common logarithm LogP of the partition coefficient P between 1-octanol and water. Although a well-known thing can be used about the method and software used for calculation of a CLogP value, in this invention, the CLOGP program incorporated in the Cambridge Soft system: Chem Draw Pro was used.

In addition, when the value of LogP of a compound differs according to a measuring method or a calculation method, it is judged by Crippen's fragmentation method whether the said compound is in the scope of the present invention.

(Solvent (auxiliary solvent) having a boiling point of 180 ° C or more)

It is preferable that boiling point is 180-260 degreeC, more preferably 180-250 degreeC, and, as for the abnormality in this invention more than 180 degreeC (hereinafter also called auxiliary solvent). Do.

The boiling point in this invention may be one type or more, and two or more types of solvents 180 degreeC or more may be sufficient as it. In the case of two or more types, the boiling point of each component should just be 180 degreeC or more.

The solvent whose boiling point is 180 degreeC or more is ethylene carbonate (EC, 261 degreeC), propylene carbonate (PC, 240 degreeC) (all made by Kanto Chemical), dipropylene glycol methyl ether (DPM, 190 degreeC), and tripropylene glycol methyl ether (TPM, 242 ° C), dipropylene glycol n-propyl ether (DPNP, 212 ° C), dipropylene glycol n-butyl ether (DPNB, 229 ° C), tripropylene glycol n-butyl ether (TPNB, 274 ° C), di Propylene glycol methyl ether acetate (DPMA, 213 ° C), propylene glycol diacetate (PGDA, 190 ° C), 1,3-butylene glycol diacetate (1,3-BGDA, 232 ° C), 1,4-butanediol diacetate (1,4-BDDA, 220 ° C), 1,6-hexanediol diacetate (1,6-HDDA, 260 ° C), dipropylene glycol methyl-n-propyl ether (DPMNP, 203 ° C), ethylene glycol monobutyl Ether acetate (BMGAC, 188 ° C), diethylene glycol monoethyl ether (EDG, 202 ° C), diethylene glycol monoethyl ether acetate (EDGAC, 217 ° C), diethylene glycol Nobutyl ether acetate (BDGAC, 247 ° C), 1,3-butylene glycol (1,3-BG, 208 ° C), triacetylene (DRA-150, 260 ° C), ethyl lactate (ELA, 181 ° C), Dipropylene glycol methyl-n-butyl ether (DPMNB, 216 degreeC) (above Daiserugagaku make) etc. are mentioned, BDGAc, ELA, 1, 3-BGDA, PGDA, PC are preferable, ELA, 1, 3-BGDA, PGDA, and PC are more preferable.

In this invention, it is preferable that a boiling point of 180 degreeC or more solvent has a partition coefficient (LogP) of -0.5-1.0 from a viewpoint of storage stability, and it is more preferable that it is -0.3-0.8. Among them, ethylene carbonate (EC, 0.3), propylene carbonate (PC, 0.62) (all manufactured by Kanto Chemical), propylene glycol diacetate (PGDA, -0.23), 1,3-butylene glycol diacetate (1,3- BGDA, 0.09), diethylene glycol monoethyl ether acetate (EDGAC, -0.02), ethyl lactate (ELA, 0.32) (above Daiserugagaku Co.) are particularly preferred.

As for content of the (C) solvent in the photosensitive resin composition of this invention, it is preferable that a boiling point of the solvent of 180 degreeC or more and the total amount of a solvent whose boiling point is less than 180 degreeC is 100-1000 weight part per 100 weight part of resin components, It is more preferable that it is 150-900 weight part, and it is more preferable that it is 200-800 weight part.

Crosslinking agent

The photosensitive resin composition of this invention contains a crosslinking agent as needed. As a crosslinking agent, the compound which has two or more epoxy groups or oxetanyl group, the alkoxy methyl group containing crosslinking agent, and the compound which has at least 1 ethylenically unsaturated double bond can be added, for example in the molecule | numerator mentioned below. By adding a crosslinking agent, a cured film can be made into a stronger film. As a crosslinking agent, the following can be added.

<Compound having two or more epoxy 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.

These are available as commercial products. For example, as bisphenol-A epoxy resin, JER827, JER828, JER834, JER1001, JER1002, JER1003, JER1055, JER1007, JER1009, JER1010 (above, Japan epoxy resin Co., Ltd.), EPICLON860, EPICLON1050, EPICLON1055 (EPICLON1055) As a bisphenol F type epoxy resin, JER806, JER807, JER4004, JER4005, JER4007, JER4010 (above, Japan epoxy resin Co., Ltd.), EPICLON830, EPICLON835 (above, DIC Corporation) Made), LCE-21, RE-602S (above, Nihon Kayaku Co., Ltd.) etc. as a phenol novolak-type epoxy resin, JER152, JER154, JER157S65, JER157S70 (above, Japan epoxy resin Co., Ltd. product) , EPICLON N-740, EPICLON N-740, EPICLON N-770, EPICLON N-775 (above, manufactured by DIC Corporation), etc. as the cresol novolac type epoxy resin, EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695 (above, made by DIC Corporation), EOCN-1020 (above, made by Nihon Kayaku Co., Ltd.), etc. As the aliphatic epoxy resin, ADEKA RESIN EP-4080S, copper ( The same is true of EP-4085S, EP-4088S (above, made by ADEKA Co., Ltd.), Ceroxide 2021P, Ceroxide 2081, Ceroxide 2083, Ceroxide 2085, EHPE3150, EPOLEAD PB 3600, Copper PB 4700 (above, Daiseru Kagaku Kogyo Co., Ltd.) etc. are mentioned. In addition, ADEKA RESIN EP-4000S, East EP-4003S, East EP-4010S, East EP-4011S (above, made by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-1000, EPPN -501, EPPN-502 (above, made by ADEKA Corporation), etc. are mentioned. These may be used alone or in combination of two or more.

Preferred among these are bisphenol A type epoxy resins, bisphenol F type epoxy resins, aliphatic epoxy resins, phenol novolac type epoxy resins, and cresol novolac type epoxy resins. In particular, a bisphenol-A epoxy resin, a phenol novolak-type epoxy resin, and an aliphatic epoxy resin are preferable.

<Compounds having two or more oxetanyl groups in the molecule>

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

1-50 weight part is preferable and, as for the addition amount of the compound which has an epoxy group or an oxetanyl group to the photosensitive resin composition, when the total amount of a resin component is 100 weight part, 3-30 weight part is more preferable.

<Alkoxymethyl group-containing crosslinking agent>

As the alkoxy methyl group-containing crosslinking agent, alkoxy methylated melamine, alkoxy methylated benzoguanamine, alkoxy methylated glycoluril, alkoxy methylated urea and the like are preferable. These can be obtained by converting the methylol group of methylolated melamine, methylolated benzoguanamine, methylolated glycoluril, or methylol group of methylolated urea into an alkoxymethyl group, respectively. The kind of the alkoxymethyl group is not particularly limited, and examples thereof include methoxymethyl group, ethoxymethyl group, propoxymethyl group, butoxymethyl group and the like. desirable. Among these crosslinkable compounds, alkoxy methylated melamine, alkoxy methylated benzoguanamine, and alkoxy methylated glycoluril are mentioned as preferable crosslinkable compounds, and alkoxy methylated glycoluril is particularly preferable from the viewpoint of transparency.

These alkoxy methyl group containing crosslinking agents are available as a commercial item, For example, Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156, 1158, 1123, 1170, 1174, UFR65, 300 (more than Mitsui Cyanamid Co., Ltd.), Nikarakku MX-750, -032, -706, -708, -40, -31, -270, -280, -290, Nikarakku MS-11, Nikarakku MW-30HM, -100LM, -390, (above, Sanwa Chemical Co., Ltd.) etc. can be used preferably.

It is preferable that it is 0.05-50 weight part with respect to 100 weight part of resin components, and, as for the addition amount of the alkoxy methyl group containing crosslinking agent when using the alkoxy methyl group containing crosslinking agent for the photosensitive resin composition of this invention, it is more preferable that it is 0.5-10 weight part. By adding in this range, preferable alkali solubility at the time of image development and the outstanding solvent resistance of the film | membrane after hardening can be obtained.

<Compounds having at least one ethylenically unsaturated double bond>

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 suitably. have.

As monofunctional (meth) acrylate, 2-hydroxyethyl (meth) acrylate, carbitol (meth) acrylate, isoboronyl (meth) acrylate, 3-methoxybutyl (meth) acryl The rate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, etc. are mentioned.

As a bifunctional (meth) acrylate, for example, ethylene glycol (meth) acrylate, 1, 6- hexanediol di (meth) acrylate, 1, 9- nonane diol di (meth) acrylate, polypropylene glycol di (Meth) acrylate, tetraethylene glycol di (meth) acrylate, bisphenoxyethanol fluorene diacrylate, bisphenoxy ethanol fluorene diacrylate, etc. are mentioned.

As (meth) acrylate more than trifunctional, for example, trimethylol propane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri ((meth) acryloyloxyethyl) phosphate, pentaerythritol tetra (Meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. are mentioned.

The compound which has at least 1 ethylenically unsaturated double bond among these can be used individually by 1 type or in combination of 2 or more types.

It is preferable that it is 50 weight part or less with respect to 100 weight part of resin components, and, as for the usage ratio of the compound which has at least 1 ethylenically unsaturated double bond in the photosensitive resin composition of this invention, it is more preferable that it is 30 weight part or less. By containing the compound which has at least 1 ethylenically unsaturated double bond in such a ratio, the heat resistance, surface hardness, etc. of the insulating film obtained from the photosensitive resin composition of this invention can be improved. When adding the compound which has at least 1 ethylenically unsaturated double bond, it is preferable to add (J) thermal radical generating agent.

Sensitizer

It is preferable that the photosensitive resin composition of this invention contains a sensitizer in order to accelerate the decomposition | disassembly in combination with a radiation sensitive acid generator. A sensitizer absorbs actinic light or a radiation and will be in an electronic excited state. The sensitizer which has become an electron-excited state comes into contact with the photoacid generator to generate an action such as electron transfer, energy transfer, and heat generation. As a result, the photoacid generator causes chemical change to decompose and generate acid. As an example of a preferable sensitizer, the compound which belongs to the following compounds, and has an absorption wavelength in either of 350 nm-450 nm of wavelength ranges is mentioned.

Polynuclear aromatics (for example, pyrene, perylene, triphenylene, anthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 3,7-dimethoxyanthracene, 9,10-dipropyloxyanthracene) ), Xanthenes (e.g. fluorescein, eosin, erythrosine, rhodamine B, rose bengal), xanthones (e.g. xanthone, thioxanthone, dimethyl thioxanthone, diethyl thioxanthone), Cyanines (e.g. thiacarbocyanine, oxacarbocyanine), Melocyanines (e.g. melocyanine, carbomelocyanine), Rhodocyanine, Oxonols, Thiazines (e.g. Thionine, methylene blue, toluidine blue), acridines (e.g. acridine orange, chloroflavin, acriflavin), acridones (e.g. acridon, 10-butyl-2-chloroa Credon), anthraquinones (e.g. anthraquinones), squalariums (e.g. squalanes), styryls, base styryls (Eg 2- [2- [4- (dimethylamino) phenyl] ethenyl] benzoxazole), coumarins (eg 7-diethylamino4-methylcoumarin, 7-hydroxy4-methylcoumarin , 2,3,6,7-tetrahydro-9-methyl-1H, 5H, 11H [1] benzopyrano [6,7,8-ij] quinolizine-11-non).

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

Adhesion improver

The photosensitive resin composition of this invention may contain a silane coupling agent as an adhesive improving agent. The silane coupling agent which can be used for the photosensitive resin composition of this invention improves the adhesiveness of the inorganic material used as a base material, for example, silicon compounds, such as silicon, a silicon oxide, and silicon nitride, metals, such as gold, copper, aluminum, and an insulating film. Compound.

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

0.1-20 weight part is preferable with respect to 100 weight part of resin components, and, as for content of the silane coupling agent in the photosensitive resin composition of this invention, 0.5-10 weight part is more preferable.

Surfactants

The photosensitive resin composition of this invention may contain surfactant. As surfactant, any of anionic, cationic, nonionic, or amphoteric can be used, but a preferable 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, silicone and fluorine-based surfactants. In the following trade names, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), F-Top (manufactured by JEMCO Corporation), Mega Pack (manufactured by DIC Corporation), Fluorine Each series, such as lard (made by Sumitomos Reem Co., Ltd.), Asahi Guard, a suffron (made by Asahi Glass Co., Ltd.), PolyFox (made by OMNOVA Corporation), is mentioned.

Moreover, the weight average molecular weight of polystyrene conversion measured by 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. The numerical value of% or more and 90 weight% or less is shown, r represents the integer of 1 or more and 18 or less, n represents the 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, From a compatibility and the wettability with respect to a to-be-coated surface, a C1-C3 alkyl group is preferable and a C2-C3 alkyl group is more preferable. Do. It is preferable that the sum (p + q) of p and q is p + q = 100, ie, 100 weight%.

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 surfactant can be used individually by 1 type or in mixture of 2 or more types.

It is preferable that the addition amount of (H) surfactant in the photosensitive resin composition of this invention is 10 weight part or less with respect to 100 weight part of resin components, It is more preferable that it is 0.01-10 weight part, It is 0.01-1 weight part More preferred.

Thermal radical generator

The photosensitive resin composition of this invention may contain the thermal radical generating agent. As the thermal radical generator in the present invention, a known thermal radical generator can be used.

A thermal radical generating agent is a compound which generate | occur | produces a radical by the energy of heat, and starts or accelerates the polymerization reaction of a polymeric compound. By adding a thermal radical generating agent, the obtained cured film becomes tough more and heat resistance and solvent resistance may improve.

Preferable thermal radical generators include aromatic ketones, onium salt compounds, organic peroxides, thio compounds, hexaarylbiimidazole compounds, ketooxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds and carbon halogens. The compound which has a bond, an azo compound, a bibenzyl compound, etc. are mentioned. A thermal radical generating agent may be used individually by 1 type, and can also use 2 or more types together.

As for the addition amount of the thermal radical generating agent in the photosensitive resin composition of this invention, when a polymer is 100 weight part, 0.01-50 weight part is preferable, 0.1-20 weight part is more preferable, It is most preferable that it is 0.5-10 weight part. Do.

Antioxidant

The photosensitive resin composition of this invention may contain antioxidant. As antioxidant, a well-known antioxidant can be contained. By adding antioxidant, coloring of a cured film can be prevented, the film thickness reduction by decomposition can be reduced, and there exists an advantage that it is excellent in heat resistance transparency.

Examples of such antioxidants include phosphorus antioxidants, hydrazides, hindered amine antioxidants, sulfur antioxidants, phenolic antioxidants, ascorbic acids, zinc sulfate, sugars, nitrites, sulfites, thiosulfates, and hydroxyls. Amine derivatives and the like. Among these, a phenolic antioxidant is especially preferable from a viewpoint of coloring of a cured film and a film thickness reduction. These may be used individually by 1 type, and may mix and use 2 or more types.

As a commercial item of a phenolic antioxidant, adecastaB AO-60, adecastab AO-80 (above, made by ADEKA Corporation), Irganox 1098 (made by Chiba Japan Co., Ltd.) is mentioned, for example. .

It is preferable that content of antioxidant is 0.1-6 mass% with respect to the total solid of the photosensitive resin composition, It is more preferable that it is 0.2-5 mass%, It is especially preferable that it is 0.5-4 mass%. By setting it as this range, sufficient transparency of the formed film can be obtained and the sensitivity at the time of pattern formation also becomes favorable.

In addition, as an additive other than antioxidant, you may add the various ultraviolet absorbers, metal deactivator, etc. which were described in "extension of polymer additives (the daily industrial newspaper)", etc. to the photosensitive resin composition of this invention.

Basic compound

The photosensitive resin composition of this invention may contain a basic compound. As a basic compound, it can select arbitrarily and can use from what is used for 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 amine include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di- Triethanolamine, dicyclohexylamine, dicyclohexylmethylamine, and the like.

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

As the heterocyclic amine, for example, 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-oxy Quinoline, pyrazine, pyrazole, pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, 1,5-diazabicyclo [4.3.0] -5-nonene, 1 , 8-diazabicyclo [5.3.0] -7-undecene, and the like.

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, Heterocyclic amine 2 It is more preferable to use together a species.

It is preferable that it is 0.001-1 weight part with respect to 100 weight part of resin components, and, as for content of the basic compound in the photosensitive resin composition of this invention, it is more preferable that it is 0.005-0.2 weight part.

(Formation method of hardened film)

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

The formation method of the cured film of this invention is characterized by including the process of the following (1)-(5).

(1) Process of applying the photosensitive resin composition of this invention on a board | substrate

(2) Process of removing solvent from applied photosensitive resin composition

(3) Process of exposing by actinic light

(4) Process of developing with developer

(5) Thermosetting process (post-baking process)

Each step will be described below in order.

In the application process of (1), the photosensitive resin composition of this invention is apply | coated (usually application | coating) on a board | substrate, and it is set as the wet film containing a solvent.

In the solvent removal process of (2), a solvent is removed and the dry film is formed on a board | substrate by pressure reduction (backing) and / or heating from said applied film.

In the exposure process of (3), actinic light of wavelength 300nm or more and 450nm or less is irradiated to the obtained coating film. In this step, (B) the photoacid generator decomposes and acid is generated. By the catalysis of the generated acid, the acid-decomposable group contained in the (A) copolymer is hydrolyzed to produce a carboxyl group or a phenolic hydroxyl group.

In the region where the acid catalyst is produced, in order to accelerate the hydrolysis reaction, post exposure bake treatment (Post Exposure Bake (hereinafter also referred to as "PEB")) can be performed as necessary. PEB can promote the production of carboxyl groups or phenolic hydroxyl groups from acid-decomposable groups.

The acid-decomposable group in the monomer unit represented by the formula (a1-1) in the present invention has a low activation energy for acid decomposition, and is easily decomposed by an acid derived from an acid generator by exposure to a carboxyl or phenolic hydroxyl group. In this case, a positive image can be formed by development without necessarily performing PEB.

In addition, by performing PEB at a relatively low temperature, hydrolysis 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 80 degrees C or less are especially preferable.

In the developing step of (4), an aqueous developer, for example, a copolymer having a free carboxyl group or a phenolic hydroxyl group is developed using an alkaline developer. A positive image is formed by removing the exposure part area | region containing the resin composition which has a carboxyl group or phenolic hydroxyl group which is easy to melt | dissolve in an alkaline developing solution.

In the post-baking step (5), the resulting positive image is heated to thermally decompose the acid-decomposable group in the monomer unit (a1) to form a carboxyl group or phenolic hydroxyl group, and crosslink with the crosslinking group of the monomer unit (a2) to form a cured film. can do. It is preferable to heat this heating at high temperature 150 degreeC or more, It is more preferable to heat at 180-250 degreeC, It is especially preferable to heat at 200-250 degreeC. Although heating time can be suitably set according to heating temperature etc., it is preferable to set it as the range of 10 to 90 minutes.

By adding a step of totally irradiating active light, preferably ultraviolet rays, to the developing pattern before the postbaking process, the crosslinking reaction can be promoted by an acid generated by actinic light irradiation.

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

<Preparation method of the photosensitive resin composition>

Various components are mixed by a predetermined ratio and by any method, stirred and dissolved to prepare a photosensitive resin composition. For example, after making each component melt | dissolve in the (C) solvent previously, these can also be mixed in a predetermined ratio and the resin composition can also be prepared. The composition solution prepared as described above may be used for use after being filtered using a filter having a pore size of 0.2 μm or the like.

<Application process and solvent removal process>

The desired dry coating film can be formed by applying 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 element, the polarizing plate, the glass plate which provided the black matrix layer, the color filter layer as needed, and provided the transparent conductive circuit layer can be illustrated. The application method to a board | substrate is not specifically limited, For example, methods, such as a slit coating method, a spray method, a roll coating method, and a spin coating method, can be used. Among them, the slit coating method is preferable from the viewpoint of being suitable for large substrates. Production from a large substrate is high and desirable. Here, a large board | substrate means the board | substrate of the magnitude | size of 1 m or more in each side.

In addition, the heating conditions of (2) solvent removal process are the ranges in which an acid-decomposable group decomposes | disassembles in the monomeric unit (a1) in the resin component in an unexposed part, and does not make a resin component soluble in an alkaline developing solution, Although it changes also with a compounding ratio, Preferably it is about 30 to 120 second at 80-130 degreeC.

<Exposure process and development process (pattern forming method)>

In an exposure process, actinic light is irradiated to the board | substrate which provided the coating film through the mask which has a predetermined pattern. After an exposure process, heat processing (PEB) is performed as needed, and in an image development process, an exposure part area | region is removed using alkaline developing solution, and an image pattern is formed.

Low-pressure mercury lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, chemical lamps, LED light sources, excimer laser generators, and the like can be used for exposure to active rays, and g-rays (436 nm), i-rays (365 nm), and h-rays (405). Active rays having a wavelength of 300 nm or more and 450 nm or less, such as nm), can be preferably used. Moreover, irradiation light can also be adjusted through a spectral filter, such as a long wavelength cut filter, a short wavelength cut filter, and a bandpass filter, as needed.

It is preferable that a basic compound is contained in the developing solution used at the image development process. As a basic compound, 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; Aqueous solutions, such as sodium silicate and sodium metasilicate, 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 developing solution is preferably 10.0 to 14.0.

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

<Post Baking Process (Crosslinking Process)>

About the pattern corresponding to the unexposed area | region obtained by image development, using heating apparatuses, such as a hotplate and oven, for a predetermined time, for example, 180-250 degreeC, for 5 to a predetermined time, for example, a hotplate If it is an oven for 60 minutes, it heat-processes for 30 to 90 minutes, decomposes the acid-decomposable group in a resin component, produces | generates a carboxyl group or phenolic hydroxyl group, reacts with a crosslinkable group in a monomer unit (a2), and crosslinks, A protective film or an interlayer insulating film having excellent 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, prior to the heat treatment, after re-exposure to the substrate on which the pattern is formed by actinic light, post-baking (re-exposure / post-baking) generates an acid from the component (B) present in the unexposed portion. It is preferable to function as a catalyst which accelerates a crosslinking process.

That is, it is preferable that the formation method of the cured film of this invention includes the re-exposure process which re-exposes by actinic light between a developing process and a postbaking 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 with respect 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>.

By the photosensitive resin composition of this invention, the interlayer insulation film which is excellent in insulation and has high transparency also when baked at high temperature can be obtained. Since the interlayer insulation film which uses the photosensitive resin composition of this invention has high transparency and is excellent in cured film physical property, it is useful for the use of an organic electroluminescence display or a liquid crystal display device.

The organic EL display device or liquid crystal display device of the present invention is not particularly limited except having a planarization film or an interlayer insulating film formed by using the photosensitive resin composition of the present invention, and various known organic EL displays having various structures. A device and a liquid crystal display device are mentioned.

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 and the interlayer insulation film, the protective film of the color filter, the spacer for maintaining the thickness of the liquid crystal layer in the liquid crystal display device, the microlenses provided on the color filter in the solid-state image sensor, and the like are preferably used. Can be.

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.

A glass substrate 6, an insulating film 3 made of Si ₃ N ₄ to form a bottom gate TFT (1) of the type and covering the TFT (1) state is formed. After forming a contact hole (not shown here) in the insulating film 3, a wiring 2 (1.0 μm in height) connected to the TFT 1 via 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 planarization layer 4 is formed on the insulating film 3 in a state of filling the unevenness of 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. In addition, 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, By providing this insulating film 8, between the 1st electrode 5 and the 2nd electrode formed in a subsequent process is provided. Short can be prevented.

Although not shown in FIG. 1, a hole transporting layer, an organic light emitting layer, and an electron transporting layer are sequentially deposited and provided through a desired pattern mask, and a second electrode made of Al is formed on the entire surface above the substrate. Active matrix type organic EL display device which is sealed by bonding using a glass plate for encapsulation and an ultraviolet curable epoxy resin, and is connected to TFTs 1 for driving them to each organic EL element. Can be 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 which has the backlight unit 12 in the back surface, and a liquid crystal panel has the all arrange | positioned between two glass substrates 14 and 15 in which the polarizing film was affixed. Elements of the TFT 16 corresponding to the pixels are arranged. In each element formed on the glass substrate, the ITO transparent electrode 19 which forms a pixel electrode is wired through the contact hole 18 formed in the cured film 17. As shown in FIG. 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 provided.

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 weights unless there is particular notice.

In the present examples, the following symbols each represent the following compounds.

V-65: 2,2'-azobis (2,4-dimethylvaleronitrile)

GMA: glycidyl methacrylate

MAA: methacrylic acid

MMA: Methyl methacrylate (made by Wako Pure Chemical Industries)

NBMA: n-butoxymethyl acrylamide (made by Tokyo Kasei)

HEMA: 2-hydroxyethyl methacrylate (made by Wako Pure Chemical Industries, Ltd.)

PGMEA: propylene glycol monomethyl ether acetate (product of Showa Denko)

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

Oxe-30: methacrylic acid (3-ethyloxetan-3-yl) methyl (manufactured by Osaka Yuga Chemical Co., Ltd.)

M100: methacrylic acid 3,4-epoxycyclohexylmethyl (made by Daiserugagaku Kogyo Co., Ltd.)

CHOEMA: 1- (cyclohexyloxy) ethyl methacrylic acid

MATHF: Methacrylic acid tetrahydrofuran-2-yl

Ph-1: α-methylhydroxystyrene

P-Ph-1: 1-ethoxyethyl protector of α-methylhydroxystyrene

St: Styrene

<Synthesis of MATHF (methacrylic acid tetrahydrofuran-2-yl)>

Methacrylic acid (86g, 1mol) was cooled to 15 degreeC, and camphorsulfonic acid (4.6g, 0.02mol) was added. 2,3-dihydrofuran (71 g, 1 mol, 1.0 equivalent) was dripped at this solution. After stirring for 1 hour, saturated aqueous sodium hydrogen carbonate solution (500 mL) was added, extracted with ethyl acetate (500 mL), dried over magnesium sulfate, and the insolubles were concentrated under reduced pressure at 40 ° C. or lower after filtration to obtain residue. The yellow oily substance was distilled under reduced pressure, and 125 g of methacrylic acid tetrahydrofuran-2-yl (MATHF) of the boiling point (bp.) 54-56 degreeC / 3.5mmHg fraction was colorless oily substance. Obtained (yield 80%).

<Synthesis of CHOEMA (1- (cyclohexyloxy) ethyl)

CHOEMA was synthesized in the same manner as in the synthesis of MAEVE.

<Synthesis of P-Ph-1 (1-ethoxyethyl protector of α-methylhydroxystyrene)>

P-Ph-1 was obtained by reacting Ph-1 with ethyl vinyl ether under an acid catalyst to obtain P-Ph-1 as an ethyl acetal protecting body of the phenolic hydroxyl group.

Synthesis of Polymer A-1

Polymer A-1 corresponding to component A of the present invention was synthesized as follows.

0.5 part of phenothiazine was added to 144.2 parts (2 molar equivalents) of ethyl vinyl ether, and 86.1 parts (1 molar equivalent) of methacrylic acid was added dropwise while cooling the reaction system to 10 ° C. or lower, followed by 4 hours at room temperature (25 ° C.). Stirred. After adding 5.0 parts of p-toluenesulfonic acid pyridinium, it stirred at room temperature for 2 hours and left to stand overnight at room temperature. 5 parts of sodium hydrogen carbonate and 5 parts of sodium sulfate were added to the reaction solution, the mixture was stirred at room temperature for 1 hour, the insolubles were concentrated under reduced pressure at 40 ° C or lower, and the yellow oily substance was distilled under reduced pressure to give a boiling point (bp.) 43 134.0 parts of 1-ethoxyethyl methacrylate of ˜45 ° C./7 mmHg fraction were obtained as colorless oil.

Obtained 1-ethoxyethyl methacrylate (63.28 parts (0.4 molar equivalent)), GMA (42.65 parts (0.3 molar equivalent)), MAA (8.61 parts (0.1 molar equivalent)), HEMA (26.03 parts (0.2 molar equivalent) ) And PGMEA (110.8 parts) were heated to 70 ° C. under a stream of nitrogen. While stirring this mixed solution, the mixed solution of radical polymerization initiator V-65 (made by Wako Pure Chemical Industries, Ltd., 4 parts) and PGMEA (100.0 parts) was dripped over 2.5 hours. After dripping was complete | finished, it was made to react at 70 degreeC for 4 hours, and the PGMEA solution (solid content concentration: 40%) of polymer A-1 was obtained.

The weight average molecular weight measured by the gel permeation chromatography (GPC) of the obtained polymer A-1 was 15,000.

<Synthesis of Polymers A-2 to A-10 and A-12 to A-21>

Polymer A-2 to A-10 and A-12 to A-21 were synthesized in the same manner as in the synthesis of Polymer A-1, except that each monomer used and its amount of use were changed to those shown in Table 1 below. . In addition, about A-10, the solvent used for synthesis | combination is diethylene glycol ethyl methyl ether (brand name: Hysorb EDM, Toho Chemical Co., Ltd. make), ethyl 3-ethoxy propionate (Daiser Chemical Co., Ltd.). All were synthesize | combined by the same method except having changed to Shikisha Co., Ltd., and it was set as A-14 and A-15, respectively. Their weight average molecular weight was the same as A-10.

Synthesis of Polymer A-11

In a three neck flask, diethylene glycol ethyl methyl ether (trade name: Hysorb EDM, manufactured by Toho Chemical Chemical Industries, Ltd., 35.7 g) was added as a solvent, and the temperature was raised to 90 ° C under a nitrogen atmosphere. To the solution, MAA (wako Pure Chemical Industries, 3.48 g), MMA (0.43 g), HEMA (0.55 g), St (12.64 g), NBMA (6.70 g), V-601 (2,2'-Azo) Bis (2-methylpropionate, Wako Pure Chemical Co., Ltd., 3.47 g, 8 mol% with respect to the monomer) was dissolved and added dropwise over 2 hours, and stirred for 2 hours after the completion of dropping. V-601 (1.84) was added to the solution. g and 2 mol%) relative to the monomer were further added, followed by further stirring for 2 hours to complete the reaction, thereby obtaining Binder A-11.

[Table 1]

The detail of the symbol which shows each compound used for the Example and the comparative example is as follows.

B-1: CGI-1397 (Compound of the structure shown below, the product made by Chiba Specialty Chemicals)

B-2: α- (p-toluenesulfonyloxyimino) phenylacetonitrile (synthetic method is shown below)

B-3: Compound of the structure shown below (synthesis method is shown below)

B-4: triphenylsulfonium nonafluorobutanesulfonate

B-5: the compound of the structure shown below (NAI-101, the product made by Midorigagaku)

C-1: ethyl lactate (ELA, Daiserugaku Co., Ltd. make, boiling point 181 degreeC, LogP = 0.32)

C-2: 1, 3- butylene glycol diacetate (1, 3-BGDA, Daiserugaku Co., Ltd. make, boiling point 232 degreeC, LogP = 0.09)

C-3: Propylene glycol diacetate (PGDA, Daiserugaku Co., Ltd. make, boiling point 190 degreeC, LogP = 0.23)

C-4: propylene carbonate (PC, Kanto Kakugaku, boiling point 240 degreeC, LogP = 0.62)

C-5: 1, 6- hexanediol diacetate (1, 6-HDDA, Daiserugaku Co., Ltd. make, boiling point 260 degreeC, LogP = 1.06)

C-6: the compound of the structure shown below (made by Tokyo Kasei Co., Ltd., LogP = -0.51)

C-7: tripropylene glycol n-butyl ether (TPNB, Daiserugagaku Co., Ltd. make, boiling point 274 degreeC, LogP = 1.46)

L-1: DBA (9,10-dibutoxy anthracene, the structure shown below, the Kawasaki Chemical Industries, Ltd. make)

E-1: JER157S65 (phenolic novolak type epoxy resin, Japan epoxy resin Co., Ltd. product)

E-2: JER828 (bisphenol A type epoxy resin, Japan epoxy resin Co., Ltd. product)

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

H-1: 1,5-diazabicyclo [4.3.0] -5-nonene (Tokyo Kasei Co., Ltd.)

H-2: triphenylimidazole (Tokyo Kasei Co., Ltd.)

H-3: Compound of the structure shown below (Toyosei Chemical Co., Ltd.)

I-1: W-3 (structure shown below, manufactured by DIC)

Bu in said formula represents a butyl group.

[Synthesis of B-2]

(Alpha)-(p-toluenesulfonyloxyimino) phenylacetonitrile was synthesize | combined according to the method of Paragraph 0108 of Unexamined-Japanese-Patent No. 2002-528451.

[Synthesis of B-3]

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 for 2 hours to react. 4 N 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 resultant was reacted at 40 ° C for 1 hour, followed by separating an aqueous solution of 2N HCl (60 mL), followed by concentration of the organic layer, and crystallization with diisopropyl ether (10 mL). The slurry was filtered, filtered and dried to obtain a ketone compound (6.5 g).

Acetic acid (7.3g) and 50weight% hydroxylamine aqueous solution (8.0g) were added and heated and refluxed to the obtained ketone compound (3.0g) and the suspension solution of methanol (30mL). 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 B-7 (2.3 g).

Further, the ¹ H-NMR spectrum (300 MHz, CDCl ₃ ) of B-3 is obtained by 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).

(Example 1)

Each component was melt | dissolved and mixed so that it might become the following composition 1, and it filtered with the polytetrafluoroethylene filter of 0.2 micrometer of diameters, and obtained the photosensitive resin composition of Example 1.

<Composition 1>

(A) Copolymer: 100.0 parts in PGMEA solution (40% of solid content) solid of polymer A-1

(B) Photoacid generator: 2.0 parts of B-1 shown above

(L) sensitizer: 2.0 parts of L-1 shown above

(C) Solvent: Ethyl lactate (ELA) 3.0 parts

(E) Crosslinking agent: 2.0 parts of E-1 shown above

(G) Adhesion improver: 0.5 parts of G-1 shown above

(H) Basic compound: 0.1 part of H-1 shown above

(H) Basic compound: 0.01 part of H-2 shown above

(I) Surfactant: 0.02 part of I-1 shown above

(Examples and Comparative Examples)

Each compound used in Example 1 was melt | dissolved and mixed with the addition amount similar to Example 1 except having changed each to the compound of the following table, and the photosensitive resin composition of the Example and the comparative example was prepared. In addition, about Examples 44-47, in addition to changing into the compound of following Table 3, the quantity of the auxiliary solvent was further added twice the amount of Example 1, and the photosensitive resin composition was adjusted. In addition, the compound was changed and evaluated as described in Table 3 below.

In Comparative Example 5, the composition described in Example 1 of JP-A-5-165214 was used. In Comparative Example 6, the composition described in Example 1 of JP-A-2004-264623 was used. In Comparative Example 7, the composition described in JP 2001-056558 A was used. In the comparative example 8, the composition of Example 1 of Unexamined-Japanese-Patent No. 2005-301210 was used.

Each evaluation shown below was performed about the photosensitive resin composition of the Example and comparative example obtained by the above.

<Evaluation of sensitivity>

After slit-coating each photosensitive resin composition on a glass substrate (Corning 1737, 0.7 mm thickness (made by Corning Corporation)), prebaking is carried out on a 90 degreeC / 120 second hotplate, the solvent is volatilized, and the film thickness 3.0 micrometers photosensitive resin composition Formed a layer.

Next, the obtained photosensitive resin composition layer was exposed through the predetermined mask using the PLA-501F exposure machine (ultra high pressure mercury lamp) by a Canon Corporation. And after developing the photosensitive resin composition layer after exposure in the alkali developing solution (0.4 weight% of tetramethylammonium hydroxide aqueous solution) for 23 degreeC / 60 second, it was rinsed with ultrapure water for 20 second.

The optimal i line | wire exposure amount (Eopt) when resolving a 10 micrometers line and space by 1: 1 by these operation was made into the sensitivity. In addition, evaluation criteria are as follows. "1" and "2" are the levels which are satisfactory practically. The results are shown in the table below.

1: Eopt less than 40mJ / ㎠

2: Eopt is more than 40mJ / ㎠ and less than 60mJ / ㎠

3: Eopt is more than 60mJ / ㎠ and less than 80mJ / ㎠

4: Eopt is more than 80mJ ／ ㎠

<Evaluation of Preservation Stability>

The sensitivity immediately after adjustment of the photosensitive resin composition was evaluated by the same method as above, and it was set as initial stage sensitivity. When the same composition was stored for one week at 30 ° C. and for two weeks, the sensitivity was measured, and the relative value of how much the change was compared with the initial sensitivity was evaluated in three steps. "1" and "2" are the levels which are satisfactory practically. The results are shown in the table below.

1: less than 5% change in sensitivity

2: 5% or more and less than 10% change in sensitivity

3: 10% or more and less than 15% change in sensitivity

4: 15% or more change in sensitivity

<Evaluation of solvent 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 of 3.0 micrometers of film thicknesses is carried out. Formed a layer.

The obtained photosensitive resin composition layer was exposed by the PLA-501F exposure machine (ultra-high pressure mercury lamp) by Canon Co., Ltd. so that accumulated irradiation amount might be 300 mJ / cm <2> (roughness: 20 mW / cm <2>, i line | wire), and this board | substrate is then oven-opened. It heated at 230 degreeC in 1 hour, and obtained the cured film.

The film thickness (T ¹ ) of the obtained cured film was measured. Subsequently, the substrate on which the cured film was formed was immersed in dimethyl sulfoxide controlled at 70 ° C. for 20 minutes, and then the film thickness t ^{1 of the} cured film after immersion was measured, and the film thickness change rate by immersion {| t ¹ -T ¹ | was calculated / T ^1} × 100 [%]. The results are shown in the following table.

When the value of the film thickness change rate is less than 1% (that is, when the result of the criteria 1-3 is obtained), the solvent resistance of a cured film can be said to be favorable.

1: The value of the film thickness change rate is less than 0.2%

2: The value of the film thickness change rate is 0.2% or more and less than 0.5%

3: The value of the film thickness change rate is 0.5% or more and less than 1%

4: The value of the film thickness change rate is 1% or more

<Evaluation of Exposure Margin>

Line exposure of the 5 μm line and space pattern after development when exposure is increased or decreased (× 1.25 and × 0.75) when exposure is performed at an exposure amount (roughness: 20 mW / cm 2, i line) at which a 10 μm line and space is obtained. The change was evaluated. The results are shown in the table below. When the line width change is less than 0.5 µm, that is, when the evaluation is "2" or less, the exposure margin can be said to be good. The results are shown in the table below.

1: line width change less than 0.3㎛

2: Line width change is 0.3 micrometer or more and less than 0.5 micrometers

3: Line width change is 0.5 micrometer or more and less than 0.7 micrometers

4: line width change is more than 0.7㎛

<Evaluation of Development Margin>

5 micrometers line and space pattern line after image development, when developing time is increased or decreased (x1.25 and x 0.75) when exposure is performed by exposure amount (roughness: 20mW / cm <2>, i line | wire) from which a 10-micrometer line and space is obtained. The line width change was evaluated. The results are shown in the table below. When the line width change is less than 0.5 µm, that is, when the evaluation is "2" or less, the exposure margin can be said to be good. The results are shown in the table below.

1: line width change less than 0.3㎛

2: Line width change is 0.3 micrometer or more and less than 0.5 micrometers

3: Line width change is 0.5 micrometer or more and less than 0.7 micrometers

4: line width change is more than 0.7㎛

<Evaluation of ITO Aptitude>

In the same manner as the evaluation of the solvent resistance, a cured film having a film thickness of 3.0 μm was formed on a glass substrate (Corning 1737, 0.7 mm thick (manufactured by Corning Corporation)). On this cured film, the ITO transparent electrode was formed by the sputter | spatter (made by ULVAC company, SIH-3030, sputter temperature 200 degreeC). The surface of the cured film after sputtering was observed with the optical microscope (500 times), and the following viewpoints evaluated.

1: no wrinkles on the surface of the cured film

2: slight wrinkles on the surface of the cured film

3: Remarkable wrinkles occur on the surface of the cured film

4: There is a crack

If significant wrinkles or cracks are observed on the surface of the cured film after the ITO transparent electrode is formed by the sputtering, the transmittance of the cured film is decreased, which is not preferable. That is, "1" and "2" are the levels which are satisfactory practically.

[Table 2]

[Table 3]

As apparent from the above table, when the composition of the present invention was used, it was found that the composition was excellent in any of sensitivity, storage stability, solvent resistance, and exposure margin.

In addition, the distribution coefficient of the auxiliary solvent of less than -0.5 tends to be slightly inferior in storage stability as compared with the best embodiment (Example 50), and 1.0 or more has higher ITO sputter resistance than the best embodiment. It was found that this tended to be slightly inferior (Example 49).

In addition, when a higher boiling point auxiliary solvent was used (for example, boiling point of 270 ° C. or more), it was found that solvent resistance tends to be slightly inferior to the best embodiment (Example 51). .

On the other hand, even when the compound containing the oxime sulfonate residue represented by general formula (b1) used the imide sulfonate compound whose structure was approximated (comparative example 4), the effect of this invention was not shown at all. Could know.

In addition, when two types were blended as a main solvent, it turned out that ITO sputter resistance improves more.

Moreover, it turned out that solvent resistance tends to improve more by mix | blending two components as a copolymer.

(Example 68)

Evaluation similar to Example 1 was changed into the ultrahigh pressure mercury lamp using the photosensitive resin composition of Example 1, and it implemented using the UV-LED light source exposure machine. As a result, the same result as in Example 1 was obtained.

(Example 69)

Except having changed the board | substrate from the glass substrate to the silicon wafer using the photosensitive resin composition of Example 21, it carried out similarly to the evaluation of the sensitivity performed about the photosensitive resin composition of Example 21, and performed sensitivity and evaluation. As a result, the same result as in Example 21 was obtained.

(Example 70)

The photosensitive resin composition of Example 11 except having changed the exposure machine into the FX-803M (gh-Line stepper) made by Nikon Corporation from the exposure machine made by Canon Corporation using the photosensitive resin composition of Example 11 The sensitivity was evaluated in the same manner as the evaluation of the sensitivity performed for. As a result, the same result as in Example 11 was obtained.

(Example 71)

The sensitivity performed with respect to the photosensitive resin composition of Example 11 except having changed the exposure machine into the 355 nm laser exposure machine from the Canon exposure machine using the photosensitive resin composition of Example 11, and performing 355 nm laser exposure. Sensitivity was evaluated in the same manner as in the evaluation. As a result, the same result as in Example 11 was obtained.

In addition, as a 355 nm laser exposure machine, "EGIS" made from V Technology Corp. was used (wavelength 355 nm, pulse width 6 nsec), and exposure amount was measured using "PE10B-V2" by OPHIR company.

As mentioned above, it turns out that the photosensitive resin composition of an Example shows the outstanding sensitivity irrespective of a board | substrate and an exposure machine.

(Example 72)

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

Forming a TFT (1) of the bottom gate type on a glass substrate 6, thereby forming the insulating film 3 made of Si ₃ N ₄ in a state covering the TFT (1). Subsequently, a contact hole (not shown) is formed in the insulating film 3, and then the wiring 2 (1.0 μm in height) connected to the TFT 1 via this contact hole is placed on the insulating film 3. Formed. 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 planarizing film 4 on the insulating film 3 is carried out by spin-coating the photosensitive resin composition of Example 31 on a board | substrate, prebaking on a hotplate (90 degreeC x 2 minutes), and using a high pressure mercury lamp on a mask. After irradiating i line | wire (365 nm) to 45mJ / cm <2> (roughness 20mW / cm <2>), it developed in alkaline aqueous solution, the pattern was formed, and heat-process for 60 minutes was performed at 230 degreeC. The applicability | paintability at the time of apply | coating this photosensitive resin composition was favorable, and generation | occurrence | production of a wrinkle and a crack were not seen in the cured film obtained after exposure, image development, and baking. In addition, 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 formed by connecting to the wiring 2 through the contact hole 7. 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. Thereafter, the resist pattern was stripped using a resist stripping solution (a mixture 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 31. By providing this insulating film, the short between the 1st electrode 5 and the 2nd electrode formed in a subsequent process can be prevented.

In addition, the hole transport layer, the organic light emitting layer, and the electron transport layer were sequentially deposited through a desired pattern mask in a vacuum vapor deposition apparatus. Then, the 2nd electrode which consists of Al was formed in the whole surface above a board | substrate. The obtained said board | substrate was taken out from the vapor deposition machine, and it sealed by bonding together 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 the organic EL element to each organic EL element was obtained. When voltage was applied through the drive circuit, it was found that the display device exhibited good display characteristics and was a highly reliable organic EL display device.

(Example 73)

In Example 72, the organic EL device was produced similarly except having replaced the photosensitive resin composition of Example 31 with the photosensitive resin composition of Example 41. It showed that favorable display characteristics were shown and it was a highly reliable organic electroluminescent display apparatus.

(Example 74)

In Example 72, the organic EL device was produced similarly except having replaced the photosensitive resin composition of Example 31 with the photosensitive resin composition of Example 51. It showed that favorable display characteristics were shown and it was a highly reliable organic electroluminescent display apparatus.

(Example 75)

In the active matrix liquid crystal display device of FIGS. 1 and 2 of JP-A-3321003, the cured film 17 was formed as an interlayer insulating film as follows to obtain a liquid crystal display device of Example 75.

That is, using the photosensitive resin composition of Example 46, the cured film 17 was formed as an interlayer insulation film by the method similar to the formation method of the planarization film 4 of the organic electroluminescent display in Example 72.

When the drive voltage was applied to the obtained liquid crystal display device, favorable display characteristics were shown and it turned out that it is a highly reliable liquid crystal display device.

(Example 76)

In Example 75, the liquid crystal display device was produced similarly except having replaced the photosensitive resin composition of Example 46 with the photosensitive resin composition of Example 56. It showed that favorable display characteristics were shown and it was a highly reliable liquid crystal display device.

(Example 77)

In Example 75, the liquid crystal display device was produced similarly except having replaced the photosensitive resin composition of Example 46 with the photosensitive resin composition of Example 66. It showed that favorable display characteristics were shown and it was a highly reliable liquid crystal display device.

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 (18)

(A) the repeating unit derived from the monomer which has a carboxyl group protected by the acid-decomposable group, and / or the repeating unit (a1) derived from the monomer which has a phenolic hydroxyl group protected by the acid-decomposable group, and the structural unit (a2) which has a crosslinking group , Polymer components contained in the same polymer and / or different polymers,
(B) a compound containing an oxime sulfonate residue represented by the following general formula (b1), and

(In General Formula (b1), R ⁵ represents an alkyl group or an aryl group.)
(C) It contains a solvent, As said solvent, At least 1 type of boiling point contains the solvent below 180 degreeC, At least 1 type of boiling point contains the solvent above 180 degreeC, and (The boiling point is a total amount of the solvent below 180 degreeC). : Photosensitive resin composition whose (boiling point total amount of solvent 180 degreeC or more) is 99: 1-50: 50 in mass conversion. The method of claim 1,
The photosensitive resin composition whose said boiling point is distribution range (LogP) of 180 degreeC or more solvent of -0.5-1.0. The method according to claim 1 or 2,
As a compound containing the said (B) oxime sulfonate residue, it selects from the group which consists of the following general formula (OS-3), general formula (OS-4), general formula (OS-5), and general formula (b2). The photosensitive resin composition containing at least 1 sort (s) which becomes.

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

(In general formula (b2), R <^5> represents an alkyl group or an aryl group, X represents an alkyl group, an alkoxy group, or a halogen atom, m represents the integer of 0-3, when m is 2 or 3, it is a plurality X may be same or different.) The method according to claim 1 or 2,
The photosensitive resin composition in which the repeating unit (a2) derived from the monomer which has the said crosslinking group contains at least 1 sort (s) chosen from the group which consists of a 3-membered ring and / or 4-membered cyclic ether residue, and ethylenically unsaturated group. The method according to claim 1 or 2,
(E) Photosensitive resin composition containing an epoxy resin further. The method according to claim 1 or 2,
As a compound containing the said (B) oxime sulfonate residue, it selects from the group which consists of the following general formula (OS-3), general formula (OS-4), general formula (OS-5), and general formula (b2). It contains at least 1 sort (s), and the repeating unit (a2) derived from the monomer which has the said crosslinking group contains at least 1 sort (s) chosen from the group which consists of a 3-membered ring and / or 4-membered cyclic ether residue, and ethylenically unsaturated group. Photosensitive resin composition.

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

(In general formula (b2), R <^5> represents an alkyl group or an aryl group, X represents an alkyl group, an alkoxy group, or a halogen atom, m represents the integer of 0-3, when m is 2 or 3, it is a plurality X may be same or different.) The method according to claim 1 or 2,
As a compound containing the said (B) oxime sulfonate residue, it selects from the group which consists of the following general formula (OS-3), general formula (OS-4), general formula (OS-5), and general formula (b2). The photosensitive resin composition containing at least 1 sort (s) made and further containing (E) epoxy resin.

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

(In general formula (b2), R <^5> represents an alkyl group or an aryl group, X represents an alkyl group, an alkoxy group, or a halogen atom, m represents the integer of 0-3, when m is 2 or 3, it is a plurality X may be same or different.) The method according to claim 1 or 2,
As a compound containing the said (B) oxime sulfonate residue, it selects from the group which consists of the following general formula (OS-3), general formula (OS-4), general formula (OS-5), and general formula (b2). Containing at least one kind, and the repeating unit (a2) derived from the monomer having the crosslinking group contains at least one kind selected from the group consisting of three- and / or four-membered cyclic ether residues and ethylenically unsaturated groups; , (E) Photosensitive resin composition containing an epoxy resin further.

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

(In general formula (b2), R <^5> represents an alkyl group or an aryl group, X represents an alkyl group, an alkoxy group, or a halogen atom, m represents the integer of 0-3, when m is 2 or 3, it is a plurality X may be same or different.) The method according to claim 1 or 2,
The repeating unit (a2) derived from the monomer which has the said crosslinking group contains at least 1 sort (s) chosen from the group which consists of a 3-membered ring and / or a 4-membered cyclic ether residue, and an ethylenically unsaturated group, and further (E) epoxy resin Photosensitive resin composition containing. The method according to claim 1 or 2,
The photosensitive resin composition which is a chemically amplified positive type photosensitive resin composition. (1) Process of applying the photosensitive resin composition of Claim 1 or 2 on a board | substrate,
(2) removing the solvent from the applied photosensitive resin composition,
(3) exposing to active radiation;
(4) developing with a developing solution, and
(5) A method of forming a cured film, comprising the step of thermosetting. The method of claim 11,
The formation method of the cured film containing the process of exposing the whole surface after the process to develop and before the process of thermosetting. The cured film formed by the formation method of the cured film of Claim 11. The cured film formed by the formation method of the cured film of Claim 12. The method of claim 13,
Cured film which is an interlayer insulation film. 15. The method of claim 14,
Cured film which is an interlayer insulation film.  The organic electroluminescence display or liquid crystal display device containing the cured film of Claim 13. The organic electroluminescence display or liquid crystal display device containing the cured film of Claim 14.

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