KR20130063479A - Method for manufacturing resin pattern using composition for micro-lends array exposer - Google Patents

Abstract

The manufacturing method of the resin pattern using the composition for microlens array exposure machines excellent in the sensitivity and the resolution. (1) Process of apply | coating the composition containing resin (A) which alkali solubility increases by the action of (A) acid, (B) oxime sulfonate system photoacid generator, and (C) solvent on a board | substrate, (2) application | coating The process of removing the said solvent from the said composition, The process of (3) irradiating actinic light to the said composition with a micro lens array exposure machine, and (4) The process of developing with the aqueous developing solution.

Description

The manufacturing method of the resin pattern using the composition for microlens array exposure machines {METHOD FOR MANUFACTURING RESIN PATTERN USING COMPOSITION FOR MICRO-LENDS ARRAY EXPOSER}

This invention relates to the manufacturing method of the resin pattern using the composition for microlens array exposure machines. In particular, it is related with the manufacturing method of the resin pattern for manufacturing a thin film transistor (TFT) substrate.

Recently, with the spread of smartphones, the wave of high-definition panels has been pushed. High-definition can be carried out on the substrate, for example, the photosensitive resin composition for forming an interlayer insulating film or Patent Document 3 described in Patent Document 1 (Japanese Patent Laid-Open No. 2004-264623) or Patent Document 2 (Japanese Patent Laid-Open No. Hei 5-165214). Although it can cope by using the stepper exposure apparatus which apply | coats the photosensitive resin composition for etching resists of Unexamined-Japanese-Patent No. 9-325473, and reduces and projects the image of a photomask with an imaging lens, for example, it is 1 m. When exposing to a board | substrate with a large area of x1m or more, there exists a problem that the lens aperture to be used becomes large corresponding to the size of a board | substrate, and becomes expensive. Regarding this problem, it is possible to produce aperiodic patterns in a large-area exposed object at high resolution by using a microlens array (MLA) exposure apparatus described in Patent Document 4 (Japanese Patent Laid-Open No. 2011-118155). It is becoming.

However, as a result of examination by the inventor of this application, it turned out that the resin pattern excellent in a sensitivity and the resolution may not be manufactured, depending on the kind of composition used for pattern formation when it exposes by MLA exposure apparatus.

This invention aims at solving the problem peculiar to MLA exposure, and provides the manufacturing method of the resin pattern excellent in the sensitivity and the resolution.

As a result of the inventor's examination on the basis of the above problems, it was found that when a composition containing a specific composition was used, no residue remained in the hole or between the exposure lines even when MLA exposure was carried out, so that a pattern excellent in sensitivity and resolution could be formed. . In particular, when the exposure is performed using a MPA exposure apparatus which has been widely used in the past, the residue may be remarkable even when the composition used in the present invention is used, but it is surprising that the residue is remarkably disappeared when the MLA exposure apparatus is used.

Specifically, the problem was solved by the following means [1], and preferably by [2] to [18].

[1] A step of applying a composition containing a resin (A) which increases alkali solubility under the action of (A) acid, (B) an oxime sulfonate-based photoacid generator, and (C) a solvent on a substrate, (3) micro The manufacturing method of the resin pattern containing the process of irradiating an active light to the said composition by the lens array exposure machine, and exposing it with (4) the aqueous developing solution.

[2] The protective phenolic according to [1], wherein the resin in which alkali solubility is increased by the action of the acid (A) is protected by a structural unit derived from a monomer having a protective carboxyl group protected by an acid decomposable group and / or an acid decomposable group. The manufacturing method of the resin pattern containing the polymer containing the structural unit (a1) derived from the monomer which has a hydroxyl group.

[3] The monomer according to [1] or [2], wherein the structural unit derived from the monomer having a protective carboxyl group protected with the acid-decomposable group and / or the protective phenolic hydroxyl group protected with an acid-decomposable group has a protective carboxyl group protected with acetal. The manufacturing method of the resin pattern which is a structural unit derived from the monomer which has a derived structural unit and / or a protective phenolic hydroxyl group protected by acetal.

[4] The structural unit and / or the following general formula in any one of [1]-[3] whose resin in which alkali solubility is increased by the action of said (A) acid is represented by the following general formula (a1-1). The manufacturing method of the resin pattern which has a structural unit represented by Formula (V).

[In Formula (a1-1), R ¹²¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, L ¹ represents a carbonyl group or a phenylene group, and R ¹²² to R ¹²⁸ each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, respectively. Indicates

[Ra ¹ to Ra ⁶ in General Formula (V) are each a hydrogen atom, an alkyl group which may have a substituent having 1 to 20 carbon atoms, or an aryl group which may have a substituent, and may be bonded to each other to form a ring. Ra ⁷ is a hydrogen atom or a methyl group, and Ra ⁸ is a halogen atom, a hydroxyl group or an alkyl group having 1 to 3 carbon atoms. n1 is an integer of 0 to 4]

[5] The production of a resin pattern according to any one of [2] to [4], wherein the resin in which alkali solubility is increased by the action of the acid (A) contains a structural unit (a2) derived from a monomer having a crosslinking group. Way.

[6] The resin according to any one of [1] to [3], wherein the alkali solubility is increased by the action of the acid (A), crosslinks the structural unit represented by the following general formula (a1-1) with a repeating unit. The manufacturing method of the resin pattern containing the polymer containing the structural unit (a2) derived from the monomer which has a group.

[In Formula (a1-1), R ¹²¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, L ¹ represents a carbonyl group or a phenylene group, and R ¹²² to R ¹²⁸ each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, respectively. Indicates

[7] The method for producing a resin pattern according to [1] to [6], further containing (D) a basic compound.

[8] The method for producing a resin pattern according to [7], wherein the basic compound (D) is a compound represented by the following General Formula (a).

Formula (a)

[In General Formula (a), R <^2> represents the linear or branched alkyl group which may have a C1-C6 substituent, or the cyclic alkyl group which may have a C3-C10 substituent. X represents an oxygen atom or a sulfur atom. Y ¹ represents an oxygen atom or an -NH- group. p1 represents an integer of 1 to 3]

[9] The resin pattern according to any one of [1] to [8], wherein the (B) oxime sulfonate-based photoacid generator is an oxime sulfonate-based acid generator represented by the following general formula (B2) or (B3). Method of preparation.

General formula (B2)

[In formula (B2), R <^42> represents an alkyl group or an aryl group, X represents an alkyl group, an alkoxy group, or a halogen atom, m4 represents the integer of 0-3, and when m4 is 2 or 3, even if several X is the same, May be different]

General formula (B3)

[In formula (B3), R <^43> represents an alkyl group or an aryl group, X <^1> represents a halogen atom, a hydroxyl group, a C1-C4 alkyl group, a C1-C4 alkoxy group, a cyano group, or a nitro group, n4 is 0-5. Represents an integer of

[10] The method for producing a resin pattern according to any one of [1] to [9], wherein the composition is a composition for an interlayer insulating film.

[11] The method for producing a resin pattern according to any one of [1] to [9], wherein the composition is a composition for etching resist.

[12] The method for producing a resin pattern according to any one of [1] to [11], wherein the composition further comprises at least one of a sensitizer, an epoxy resin, an adhesion improving agent, a basic compound, and a surfactant.

[13] The method for producing a resin pattern according to any one of [1] to [12], further comprising a step of postbaking after the step of developing with the aqueous developer (4).

[14] A method for producing the resin pattern according to any one of [1] to [12], wherein the substrate is etched using (5) the formed resin pattern as a mask after the step of developing with (4) the aqueous developer. Process and a manufacturing method of a pattern board | substrate including (6) the process of peeling the said resin pattern.

[15] The method for producing a patterned substrate according to [14], wherein the resin in which alkali solubility is increased by the action of the acid (A) has a structural unit represented by the general formula (V) as a repeating unit.

[16] A method for producing an interlayer insulating film, comprising the method for producing a resin pattern according to any one of [1] to [13].

[17] a method for producing the resin pattern according to any one of [1] to [13], a method for producing a pattern substrate according to [14] or [15], or a method for producing an interlayer insulating film according to [16]. Method of manufacturing a thin film transistor substrate.

[18] a method for producing the resin pattern according to any one of [1] to [13], a method for producing a pattern substrate according to [14] or [15], or a method for producing an interlayer insulating film according to [16]. Method for manufacturing a display device.

(Effects of the Invention)

Even if MLA exposure is performed by this invention, preparation of the resin pattern excellent also in the sensitivity and the resolution was attained.

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, in this specification, "-" is used by the meaning which includes the numerical value described before and after that as a lower limit and an upper limit. In this specification, unless otherwise indicated, "group", such as an alkyl group, may have a substituent, and does not need to have it.

[Method for Producing Resin Pattern]

The manufacturing method of the resin pattern of this invention is

(1) Process of apply | coating the composition containing resin which (A) acid solubility increases by action of acid, (B) oxime sulfonate system photoacid generator, and (C) solvent on board | substrate,

(2) removing the solvent from the applied composition;

(3) exposing the composition to irradiated actinic light with a microlens array exposure machine, and

(4) The process of developing with aqueous developing solution is included.

As a result of the present inventor's examination, when a well-known photosensitive resin composition was exposed by MLA exposure apparatus, it turned out that a residue remains in a hole easily. According to 1st Embodiment of the manufacturing method of the resin pattern of this invention mentioned later, even if it exposes by MLA exposure apparatus, the residue in a hole can be eliminated and a sensitivity and a resolution can be made favorable.

Moreover, as a result of this inventor's examination, it turns out that a residue is easy to remain between exposure lines when it exposes in a well-known photosensitive resin composition by MLA exposure apparatus. According to 2nd Embodiment of the manufacturing method of the resin pattern of this invention mentioned later, even if it exposes by MLA exposure apparatus, the residue between exposure lines can be eliminated, and a sensitivity and a resolution can be made favorable.

Hereinafter, the preferable aspect of the manufacturing method of the resin pattern of this invention is demonstrated in order of 1st Embodiment and 2nd Embodiment.

[First Embodiment of Manufacturing Method of Resin Pattern]

It is preferable that the manufacturing method of the resin pattern of this invention further includes the process of (5) post-baking after the process of developing with (4) aqueous developing solution in addition to the process of said (1)-(4), for example. In addition, it is preferable to apply 1st Embodiment to the manufacturing method of an interlayer insulation film.

(1) Process of apply | coating composition on board | substrate

In the application | coating process of (1), it is preferable to set it as the wet membrane which apply | coats a composition on a board | substrate and contains a solvent. Hereinafter, the process after the application | coating process of (1) is demonstrated about a composition.

[Composition]

The composition used by this invention contains resin (A) which alkali solubility improves by the effect | action of an acid, (B) oxime sulfonate type photo-acid generator, and (C) solvent.

It is preferable that it is positive type, and, as for the composition used by this invention, it is more preferable that it is positive type of a chemical amplification type.

EMBODIMENT OF THE INVENTION Hereinafter, preferred embodiment of each component is described in order about the composition used by this invention.

&Lt; Component (A) >

The composition used by this invention has a structural unit derived from the monomer which has a protective carboxyl group protected by the acid-decomposable group as the (A) component, or a structural unit (a1) derived from the monomer which has a protective phenolic hydroxyl group protected by the acid-decomposable group, and a crosslinking group. The polymer containing the structural unit (a2) derived from a monomer is contained.

That is, the (A) polymer which the composition used by this invention contains preferably

(a1) a repeating unit derived from a monomer having a protective carboxyl group protected with an acid-decomposable group or a repeating unit derived from a monomer having a protective phenolic hydroxyl group protected with an acid-decomposable group (hereinafter also referred to as a "repeating unit derived from a monomer (a1)"); ,

(a2) A polymer containing a repeating unit derived from a monomer having a crosslinking group (hereinafter also referred to as "a repeating unit derived from a monomer (a2)").

The component (A) may contain a repeating unit (a3) derived from another monomer in addition to the repeating unit (a1) derived from the monomer and the repeating unit (a2) derived from the monomer.

It is preferable that (A) polymer is alkali-insoluble, and it is preferable that it is resin which becomes alkali-soluble when the acid-decomposable group which the repeating unit (a1) derived from a monomer decompose | disassembles. Here, an acid-decomposable group shows the functional group which can decompose in presence of an acid. That is, the repeating unit derived from the monomer which has the protective carboxyl group in which the carboxyl group was protected by the acid-decomposable group can produce | generate a carboxyl group by decomposing a protecting group by an acid, and also the monomer which has a protective phenolic hydroxyl group in which a phenolic hydroxyl group was protected by the acid-decomposable group. The derived repeating unit can generate a phenolic hydroxyl group by decomposing a protecting group by an acid. In the present invention, "alkali solubility" refers to a coating film (thickness 3 µm) of the compound (resin) formed by applying a solution of the compound (resin) onto a substrate and heating the substrate at 90 ° C. for 2 minutes. The dissolution rate in the 0.4% tetramethylammonium hydroxide aqueous solution is 0.01 µm / sec or more, and “alkali insoluble” is formed 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 (thickness 3 micrometers) of the said compound (resin) becomes less than 0.01 micrometer / sec.

The said (A) polymer may have a repeating unit derived from the carboxyl group mentioned later, the structure derived from carboxylic anhydride, and / or the other monomer which has phenolic hydroxyl group, etc. However, when introducing an acidic group, it is preferable to introduce in the range which keeps the said (A) polymer whole in alkali insoluble.

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

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

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

Hereinafter, each of the repeating unit (a1) derived from a monomer and the repeating unit (a2) derived from a monomer is demonstrated.

<< repeating unit derived from the monomer which has a protective carboxyl group protected by the acid-decomposable group, or repeating unit derived from the monomer which has a protective phenolic hydroxyl group protected by the acid-decomposable group >>

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

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

<<< repeat unit derived from the monomer which has the protective carboxyl group protected by the (a1-1) acid-decomposable group >>>

The repeating unit (a1-1) derived from the monomer which has the protective carboxyl group protected by the said acid-decomposable group is a monomer which has the protective carboxyl group protected by the acid-decomposable group demonstrated in detail below by the said carboxyl group of the repeating unit derived from the monomer which has a carboxyl group. It is a repeating unit of origin.

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

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

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

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

Especially, in order to form the repeating unit (a1-1-1) derived from the monomer derived from unsaturated carboxylic acid etc. which have at least 1 carboxyl group in the said molecule from a developable viewpoint, acrylic acid, methacrylic acid, or unsaturated polyhydric carboxylic acid It is preferable to use anhydride, etc., and it is more preferable to use acrylic acid or methacrylic acid.

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

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

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

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

The reaction rate with respect to the hydroxyl group of the said acid anhydride is preferably 10-100 mol%, More preferably, it is 30-100 mol% from a developable viewpoint.

Acid decomposable group >>>> which can be used for repeating unit (a1-1) derived from <<<< monomer

As said acid-decomposable group which can be used for the repeating unit (a1-1) derived from the monomer which has the protective carboxyl group protected by the said acid-decomposable group, it is known so far as an acid-decomposable group in the positive resist for KrF and the positive resist for ArF. It can use and it does not specifically limit. Conventionally, as an acid-decomposable group, a group (e.g., an acetal functional group such as tetrahydropyranyl group) that is relatively easy to decompose by an acid, or a group (e.g., a t-butyl ester group or t-) that is relatively hard to decompose by an acid T-butyl functional groups, such as a butyl carbonate group) are known.

Among these acid decomposable groups, the carboxyl group is a repeating unit derived from a monomer having a protective carboxyl group protected by acetal or ketal or a carboxyl group protected by ketal, and the basic physical properties of the resist, in particular, the sensitivity, pattern shape, and formation of contact holes. It is preferable from the viewpoint of the storage stability and the composition. Moreover, it is more preferable from a viewpoint of a sensitivity that a carboxyl group is a protective carboxyl group protected by the acetal or ketal represented by the following general formula (a1-1) among acid-decomposable groups. In the case where the carboxyl group is a protective carboxyl group protected with acetal or ketal represented by the following general formula (a1-1), the whole of the protective carboxyl group has a structure of-(C = O) -O-CR ¹⁰¹ R ¹⁰² (OR ¹⁰³ ). It is.

General formula (a1-1)

[Formula (a1-1) of R ¹⁰¹ and R ¹⁰² each represents a hydrogen atom or an alkyl group, other than a case in which only R ¹⁰¹ and R ¹⁰² is a hydrogen atom together. R ¹⁰³ represents an alkyl group. R ¹⁰¹ or R ¹⁰² may be linked to R ¹⁰³ to form a cyclic ether.]

In said general formula (a1-1), R <^101> -R <^103> represents a hydrogen atom or an alkyl group, respectively, and the said alkyl group may be any of linear, branched, and cyclic | annular. Both R ¹⁰¹ and R ¹⁰² do not represent a hydrogen atom, and at least one of R ¹⁰¹ and R ¹⁰² represents an alkyl group.

In the general formula (a1-1), when R ¹⁰¹ , R ¹⁰² and R ¹⁰³ represent an alkyl group, the alkyl group may be linear, branched or cyclic.

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

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

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

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

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

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

Moreover, when the said alkyl group is a cycloalkyl group, the said cycloalkyl group may have a C1-C10 linear or branched alkyl group as a substituent, and when a alkyl group is a linear or branched alkyl group, it is C3-C12 as a substituent. May have two cycloalkyl groups.

These substituents may further be substituted by the said substituent.

When R <^101> , R <^102> and R <^103> represent an aryl group in the said general formula (a1-1), 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 preferably illustrate a C1-C6 alkyl group as said substituent. As an aryl group, a phenyl group, a tril group, a silyl group, cumenyl group, 1-naphthyl group etc. can be illustrated, for example.

In addition, R ¹⁰¹ , R ¹⁰² and R ¹⁰³ may be bonded to each other to form a ring together with the carbon atom to which they are bonded. Examples of the ring structure in the case where R ¹⁰¹ and R ¹⁰² , R ¹⁰¹ and R ^103, or R ¹⁰² and R ¹⁰³ combine with each other include cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, tetrahydrofuranyl group, and And a dantilyl group and a tetrahydropyranyl group.

In formula (a1-1), one of R ¹⁰¹ and R ¹⁰² is preferably a hydrogen atom or a methyl group.

A commercially available radical may be used for the radically polymerizable monomer used in order to form the repeating unit derived from the monomer which has a protective carboxyl group represented by said general 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 acid catalyst as shown below.

R ¹¹¹ in the scheme represents a hydrogen atom or an alkyl group, and the alkyl group is the same as the alkyl group represented by R ¹⁰¹ to R ¹⁰³ in General Formula (a1-1). As R ^{111, a} hydrogen atom or a methyl group is preferable.

R ¹¹² and R ^{113 are} —CH (R ¹¹² ) (R ¹¹³ ), which are the same as those in R ¹⁰² in General Formula (a1-1), and R ¹¹⁴ in R ¹⁰¹ in General Formula (a-1). and accept a, R ¹¹⁵ is R ^103, and accept in the general formula (a1-1), which also is a preferred range of the same.

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

As for the repeating unit (a1-1) derived from the monomer which has the protective carboxyl group protected by the said acid-decomposable group, the structural unit of the following general formula is preferable.

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

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

<<< repeat unit derived from the monomer which has the protective phenolic hydroxyl group protected by the (a1-2) acid-decomposable group >>>

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

Repeating unit >>>> derived from the monomer which has <<<< (a1-2-1) phenolic hydroxyl group

As a repeating unit derived from the monomer which has the said phenolic hydroxyl group, the repeating unit derived from a hydroxy styrene-type monomer, and the repeating unit derived from the monomer in novolak-type resin are mentioned, Among these, it originates from (alpha) -methylhydroxy styrene. The repeating unit derived from the monomer used is preferable from a viewpoint of transparency. Among the repeating units derived from the monomer which has a phenolic hydroxyl group, the repeating unit derived from the monomer represented by the following general formula (a1-2) is preferable from a viewpoint of transparency and a sensitivity.

General formula (a1-2)

[In general formula (a1-2), R ²²⁰ represents a hydrogen atom or a methyl group, R ²²¹ represents a single bond or a divalent linking group, R ²²² represents a halogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms. a represents the integer of 1-5, b represents the integer of 0-4, and a + b is 5 or less. In addition, when two or more R <^222> exists, these R <^222> may mutually differ or may be the same.]

R ²²⁰ in the general formula (a1-2) represents a hydrogen atom or a methyl group, and is preferably a methyl group.

In addition, R ²²¹ represents a single bond or a divalent linking group. In the case of a single bond, since sensitivity can be improved and transparency of a cured film can be improved, it is preferable. Examples of the divalent linking group for R ²²¹ include an alkylene group, and specific examples in which R ²²¹ is an alkylene group include a methylene group, an ethylene group, a propylene group, an isopropylene group, an n-butylene group, an isobutylene group, a tert-butylene group, Pentylene group, isopentylene group, neopentylene group, hexylene group, etc. are mentioned. Especially, it is preferable that R <^221> is a single bond, a methylene group, and an ethylene group. The divalent linking group may have a substituent, and examples of the substituent include a halogen atom, a hydroxyl group, and an alkoxy group.

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

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

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

B represents 0 or an integer of 1 to 4;

Among the repeating units derived from the monomer having a phenolic hydroxyl group, when R ²²¹ is not an alkylene group in the general formula (a1-2), the repeating unit derived from the monomer represented by the following general formula (a1-2 ') has transparency and sensitivity. More preferable from the viewpoint of. As the linking group for R ^221, an alkyleneoxycarbonyl group or the like (from the side of the main chain of the polymer) can be preferably illustrated in addition to the alkylene group.

General formula (a1-2 ')

[In Formula (a1-2 '), R ²³⁰ is synonymous with R ²²⁰ in the formula (a1-2), R ²³² is synonymous with R ²²² in Formula (a1-2), and a1 and b1 is synonymous with a and b in the said general formula (a1-2), respectively. In addition, the preferable range is also the same]

R <^233> in the said general formula (a1-2 ') represents a bivalent coupling group, 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 an ethylene group, a propylene group, an isopropylene group, an n-butylene group, a tert-butylene group, a pentylene group, and 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, R ²³³ is preferably an ethylene group, a propylene group, or a 2-hydroxypropylene group from the viewpoint of sensitivity.

Acid decomposable group >>>> which can be used for repeating unit (a1-2) derived from <<<< monomer

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

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

Moreover, as a radically polymerizable monomer used in order to form the repeating unit derived from the monomer which a phenolic hydroxyl group has the protective phenolic hydroxyl group protected by acetal or ketal, the 1-alkoxyalkyl protecting body of hydroxystyrene, hydroxy, for example Tetrahydropyranyl protector of styrene, 1-alkoxyalkyl protector of α-methyl-hydroxystyrene, tetrahydropyranyl protector of α-methyl-hydroxystyrene, 1- of 4-hydroxyphenylmethacrylate Alkoxyalkyl protector, tetrahydropyranyl protector of 4-hydroxyphenyl methacrylate, 1-alkoxyalkyl protector of 4-hydroxybenzoic acid (1-methacryloyloxymethyl) ester, 4-hydroxybenzoic acid Tetrahydropyranyl protector of (1-methacryloyloxymethyl) ester, 1-alkoxyalkyl protector of 4-hydroxybenzoic acid (2-methacryloyloxyethyl) ester, 4-hydroxybenzoic acid (2 Methacryl Tetrahydropyranyl protector of yloxyethyl) ester, 1-alkoxyalkyl protector of 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester, 4-hydroxybenzoic acid (3-methacryloyloxy Tetrahydropyranyl protector of propyl) ester, 1-alkoxyalkyl protector of 4-hydroxybenzoic acid (3-methacryloyloxy-2-hydroxypropyl) ester, 4-hydroxybenzoic acid (3-methacryl) The tetrahydropyranyl protecting body of royloxy-2-hydroxypropyl) ester, etc. are mentioned.

Of these, 1-alkoxyalkyl protecting group of 4-hydroxyphenyl methacrylate, tetrahydropyranyl protecting group of 4-hydroxyphenyl methacrylate, 4-hydroxybenzoic acid (1-methacryloyloxymethyl) ester 1 of the 1-alkoxyalkyl protecting agent, tetrahydropyranyl protecting agent of 4-hydroxybenzoic acid (1-methacryloyloxymethyl) ester, and 4-hydroxybenzoic acid (2-methacryloyloxyethyl) ester -Alkoxyalkyl protector, tetrahydropyranyl protector of 4-hydroxybenzoic acid (2-methacryloyloxyethyl) ester, 1-alkoxy of 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester Alkyl protecting agent, tetrahydropyranyl protecting agent of 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester, 4-hydroxybenzoic acid (3-methacryloyloxy-2-hydroxypropyl) ester 1-alkoxyalkyl protector, 4-hydroxybenzoic acid (3-methacryloyloxy-2-hi Hydroxy-propyl) are preferred from the viewpoint of transparency, tetrahydropyranyl carbonyl protecting body of the ester.

Specific examples of the acetal protecting group and the ketal protecting group of the phenolic hydroxyl group include 1-alkoxyalkyl groups, 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.

The radically polymerizable monomer used in order to form the repeating unit (a1-2) derived from the monomer which has the protection phenolic hydroxyl group protected by the said acid-decomposable group may use a commercially available thing, and may use the thing synthesize | combined by a well-known method. have. For example, the compound having a phenolic hydroxyl group can be synthesized by reacting with vinyl ether in the presence of an acid catalyst. The 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 acid catalyst after that.

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

<<< preferred embodiment of the repeating unit (a1) derived from other monomers >>>

The content rate of the repeating unit (a1) derived from a monomer among the repeating units derived from the monomer which comprises the sum total of the said polymer (A ') and a polymer (A') or a polymer (A) (preferably said (A) polymer) is a sensitivity. From the standpoint of the polymer as a whole, 3 to 70 mol% is preferable, and 5 to 60 mol% is more preferable. Moreover, especially when the said acid-decomposable group which can be used for the repeating unit (a1) derived from the said monomer is a repeating unit derived from the monomer which has a protective carboxyl group in which a carboxyl group was protected by acetal, or a carboxyl group protected by ketal, the monomer derived from a monomer. As for the content rate of the repeating unit (a1) derived from the monomer in the repeating unit derived from the monomer which comprises the polymer containing a unit (a1), 10-50 mol% is more preferable.

The repeating unit (a1-1) derived from the monomer having a protective carboxyl group protected with the acid-decomposable group is faster than the repeating unit (a1-2) derived from the monomer having a protective phenolic hydroxyl group protected with the acid-decomposable group. There is this. Therefore, when developing rapidly, the repeating unit (a1-1) derived from the monomer which has the protective carboxyl group protected by the acid-decomposable group is preferable. On the contrary, in order to slow development, it is preferable to use the repeating unit (a1-2) derived from the monomer which has the protective phenolic hydroxyl group protected by the acid-decomposable group.

<< repeating unit derived from the monomer which has a (a2) crosslinking group >>

It is preferable that (A) component has a repeating unit (a2) derived from the monomer which has 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 embodiment of the repeating unit derived from the monomer which has a preferable crosslinking group, the repeating unit derived from the monomer containing at least 1 selected from the group which consists of an oxiranyl group, an oxetanyl group, and an ethylenically unsaturated group is mentioned. That is, the repeating unit derived from the monomer containing at least 1 selected from the group which consists of a 3-membered ring and / or a 4-membered ring cyclic ether group, and ethylenically unsaturated group is mentioned. Especially, it is more preferable that the composition used by this invention contains the repeating unit derived from the monomer in which the said (A) component contains at least 1 of an oxiranyl group and an oxetanyl group, and originates in the monomer containing an oxetanyl group. It is especially preferable to include the repeating unit of. In more detail, the following are mentioned.

<<< repeat unit derived from the monomer which has (a2-1) oxiranyl group and / or oxetanyl group >>>

It is preferable that the said (A) polymer contains the repeating unit (repeating unit (a2-1) derived from a monomer) derived from the monomer which has an oxiranyl group and / or an oxetanyl group. The three-membered ring cyclic ether group is also called an oxiranyl group, and the four-membered ring cyclic ether group is also called an oxetanyl group. As a repeating unit (a2-1) derived from the monomer which has the said oxiranyl group and / or oxetanyl group, it is preferable that it is a repeating unit derived from the monomer which has an alicyclic oxiranyl group and / or an oxetanyl group, and has an oxetanyl group It is more preferable that it is a repeating unit derived from a monomer.

The repeating unit (a2-1) derived from the monomer which has the said oxiranyl group and / or oxetanyl group should just have at least one oxiranyl group or an oxetanyl group in the repeating unit derived from one monomer, and one or more oxy It may have a ranyl group and one or more oxetanyl groups, two or more oxiranyl groups, or two or more oxetanyl groups, although it is not specifically limited, It is preferable to have one or three oxiranyl groups and / or oxetanyl groups in total. And it is more preferable to have one or two oxiranyl group and / or oxetanyl group in total, and it is still more preferable to have one oxiranyl group or oxetanyl group.

As a specific example of the radically polymerizable monomer used in order to form the repeating unit derived from the monomer which has an oxiranyl group, For example, glycidyl acrylate, glycidyl methacrylate, the glycidyl (alpha)-ethyl acrylate, the (alpha) -n-propyl Glycidyl acrylate, α-n-butyl acrylate glycidyl, acrylic acid-3,4-epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6, 7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, Japanese Patent No. 4168443 The compound containing the alicyclic epoxy skeleton of Paragraph 0031-0035 of this etc. is mentioned.

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

As a specific example of the radically polymerizable monomer used in order to form the repeating unit (a2-1) derived from the monomer which has the said oxiranyl group and / or oxetanyl group, it contains the monomer containing a methacrylic acid ester structure, and an acrylic acid ester structure. It is preferable that it is a monomer to make.

More preferred among these monomers include a compound containing an alicyclic epoxy skeleton described in paragraphs 0034 to 0035 of JP 4168443 and an oxetanyl group described in paragraphs 0011 to 0016 of JP 2001-330953 A. It is a (meth) acrylic acid ester and it is a (meth) acrylic acid ester which has an oxetanyl group as described in Paragraph 0011-0016 of Unexamined-Japanese-Patent No. 2001-330953. Among these, preferred are 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, acrylic acid (3-ethyloxetan-3-yl) methyl, and methacrylic acid (3-ethyloxetane- 3-yl) methyl, most preferred are acrylic acid (3-ethyloxetan-3-yl) methyl and methacrylic acid (3-ethyloxetan-3-yl) methyl. The repeating unit derived from these monomers can be used individually by 1 type or in combination of 2 or more types.

The repeating unit (a2-1) derived from the monomer which has the said oxiranyl group and / or oxetanyl group has a structure selected from the group which consists of following formula (a2-1-1) and formula (a2-1-2). desirable.

It is a formula (a2-1) that the repeating unit (a2-1) derived from the monomer which has the said oxiranyl group and / or oxetanyl group has either of three structures represented by said formula (a2-1-1). It shows what has group except one or more hydrogen atoms from the structure represented by -1).

The repeating unit (a2-1) derived from the monomer which has the said oxiranyl group and / or oxetanyl group has a 3, 4- epoxycyclohexyl group, a 2, 3- epoxycyclohexyl group, and a 2, 3- epoxycyclopentyl group More preferred.

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

In said general formula (a2-1-2), R <^1b> and R <^6b> represent a hydrogen atom or an alkyl group, respectively, It is preferable that they are a hydrogen atom or a C1-C8 alkyl group, and a hydrogen atom or a C1-C5 alkyl group (following) 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 represent a hydrogen atom, a halogen atom, an alkyl group or an aryl group.

As said 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 still more preferable.

The alkyl group may be linear, branched or 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 further more preferable that it is C1-C4. The cyclic alkyl group preferably has 3 to 10 carbon atoms, more preferably 4 to 8 carbon atoms, and still more preferably 5 to 7 carbon atoms. 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 said 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 represent a hydrogen atom, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group or a perfluoro carbon having 1 to 4 carbon atoms. It is more preferable that it is an alkyl group.

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

As a preferable specific example of the repeating unit (a2-1) derived from the monomer which has the said oxiranyl group and / or oxetanyl group, the repeating unit derived from the following monomer can be illustrated. R represents a hydrogen atom or a methyl group.

In this invention, an oxetanyl group is preferable among an oxiranyl group and / or an oxetanyl group from a viewpoint of hardening sensitivity. Moreover, in this invention, an alicyclic oxiranyl group and an oxetanyl group are preferable from a viewpoint of a transmittance | permeability (transparency). As mentioned above, in this invention, as an oxiranyl group and / or an oxetanyl group, an alicyclic oxiranyl group and an oxetanyl group are preferable, and an oxetanyl group is especially preferable.

<<< repeat unit derived from the monomer which has a (a2-2) ethylenically unsaturated group >>>

As one of the repeating units (a2) derived from the monomer which has the said crosslinking group, the repeating unit (a2-2) derived from the monomer which has an ethylenically unsaturated group is mentioned (henceforth "the repeating unit (a2-2) derived from a monomer"). do). As a repeating unit (a2-2) derived from the monomer which has the said ethylenically unsaturated group, the repeating unit derived from the monomer which has an ethylenically unsaturated group in a side chain is preferable, has a ethylenically unsaturated group at the terminal, and has a C3-C16 side chain The repeating unit derived is more preferable, and the repeating unit derived from the monomer which has a side chain represented by following General formula (a2-2-1) is more preferable.

General formula (a2-2-1)

[In Formula (a2-2-1), R ³⁰¹ represents a divalent linking group having 1 to 13 carbon atoms, R ³⁰² represents a hydrogen atom or a methyl group, and * represents a main chain of a repeating unit (a2) derived from a monomer having a crosslinking group. Indicates the site to be connected to]

R ³⁰¹ is a C1-C13 divalent linking group, which may include an alkenyl group, an arylene group, or a combination thereof, and may include a bond such as an ester bond, an ether bond, an amide bond, or a urethane bond. The alkenyl group may be any one of linear, branched or cyclic alkenyl groups. In addition, the divalent linking group may have substituents, such as a hydroxyl group and a carboxyl group, in arbitrary positions. Specific examples of R ³⁰¹ include the following divalent linking groups.

Among the side chains represented by general formula (a2-2-1), aliphatic side chains are preferable including the divalent linking group represented by R ³⁰¹ . Of the side chains having a linking group represented by the general formula (a2-2-1), a terminal represented by -CH (R ³⁰² ) = CH ₂ connecting through a divalent linking group represented by R ³⁰¹ is a methacryloyl group It is more preferable that it is a phosphorus side chain, ie, said R <^302> is a methyl group.

In addition, the ethylenically unsaturated group contained in the side chain represented by the said general formula (a2-2-1) is the sum total of the said polymer (A ') and a polymer (A'), or a polymer (A) (preferably said (A) It is preferable that 1 mol is contained with respect to 150-2,000 g with respect to a polymer), and it is more preferable that 1 mol is contained with respect to 200-1,300 g.

In this invention, it is preferable that the repeating unit (a2-2) derived from the monomer which has the said ethylenically unsaturated group is a repeating unit derived from the monomer represented by the following general formula (a2-2-2).

General formula (a2-2-2)

[R <^311> in general formula (a2-2-2) is synonymous with R < ³⁰¹ > in the said general formula (a2-2-1), and its preferable range is also the same. R ³¹² and R ³¹³ each represent a hydrogen atom or a methyl group]

Although the method of obtaining the repeating unit (a2-2) derived from the monomer which has a side chain represented by said general formula (a2-2-1) is not specifically limited, For example, it has a specific functional group previously by polymerization methods, such as radical polymerization. Derived from a monomer having a side chain represented by the general formula (a2-2-1) by producing a polymer and reacting a compound having an ethylenically unsaturated group (hereinafter referred to as a specific compound) to the group and the terminal that react with the specific functional group. It can be set as the polymer which has a repeating unit (a2-2).

As said specific functional group, a carboxyl group, an epoxy group, a hydroxyl group, the amino group which has active hydrogen, a phenolic hydroxyl group, an isocyanate group, etc. are mentioned here. 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, a combination of a carboxyl group and an epoxy group, a combination of a carboxyl group and an oxetanyl group, a combination of a hydroxy group and an isocyanate group, a combination of a phenolic hydroxyl group and an epoxy group, a carboxyl group and an isocyanate Combinations of groups, combinations of amino groups and isocyanate groups, combinations of hydroxy groups and acid chlorides, and the like.

Moreover, as said specific compound, glycidyl methacrylate, glycidyl acrylate, 3, 4- epoxy cyclohexyl methyl methacrylate, 3, 4- epoxy cyclohexyl methyl acrylate, isocyanate ethyl methacrylate, isocyanate ethyl Acrylate, methacrylic acid chloride, acrylic acid chloride, methacrylic acid, acrylic acid and the like.

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

Although the specific example of the monomer which has the said specific functional group required in order to obtain the polymer which has the said specific functional group is shown below, 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 the said epoxy group, for example, glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, 3-ethenyl-7-oxabicyclo [4.1.0] heptane, 1,2-epoxy -5-hexene, 1,7- octadiene monoepoxide, 3, 4- epoxycyclohexyl methyl methacrylate, 3, 4- epoxycyclohexyl methyl acrylate, etc. are mentioned.

As a monomer which has the said hydroxy group, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, for example. , 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-hydroxy norbornene-2-carboxylic-6-lactone, 5-methacryloyloxy-6-hydroxy norbornene-2-carboxylic-6-lactone, and the like.

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

As a monomer which has the said 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 the said isocyanate group, acryloyl ethyl isocyanate, methacryloyl ethyl isocyanate, m- tetramethyl xylene isocyanate, etc. are mentioned, for example.

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

Although the method of obtaining the polymer which has the said specific functional group used by 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 desired, It is obtained by polymerizing under temperature. The solvent used in that case will not be specifically limited if it melt | dissolves the monomer which comprises the polymer which has a specific functional group, and the polymer which has a specific functional group. 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.

Next, the repeating unit (a2-2) derived from the monomer which has an ethylenically unsaturated group in the terminal of a side chain can be obtained by making the polymer and specific compound which have the obtained specific functional group react. Usually, the solution of the polymer which has a specific functional group then is provided to reaction. For example, the repeating unit (a2-2) derived from a monomer by making glycidyl methacrylate react at the temperature of 80 degreeC-150 degreeC in the presence of catalysts, such as benzyl triethylammonium chloride, in the solution of the acrylic polymer which has a carboxyl group. Can be obtained.

In addition, in order to form the repeating unit (a2-2) derived from a monomer, you may use allyl methacrylate, allyl acrylate, etc. as a radically polymerizable monomer other than using the above-mentioned polymer reaction. The repeating unit derived from these monomers can be used individually or in combination of 2 or more types.

<<< preferred embodiment of the repeating unit (a2) derived from a monomer >>>

The content of the repeating unit (a2) derived from a monomer among the repeating units derived from the monomer which comprises the sum total of the said polymer (A ') and a polymer (A'), or a polymer (A) (preferably said (A) polymer) is formed 5-60 mol% is preferable from a viewpoint of the various tolerances and transparency of a film | membrane, 10-55 mol% is more preferable, and 20-50 mol% is still more preferable. If it is in the range of the said numerical value, transparency of the cured film obtained from a composition and ITO sputter resistance will become favorable.

<< (a3) repeating unit derived from other monomers >>

In this invention, (A) component may have a repeating unit (a3) derived from other monomers except the repeating unit (a1) derived from the said monomer, and (a2). As a monomer used as the repeating unit (a3) derived from another monomer, styrene, (meth) acrylic-acid alkylester, (meth) acrylic-acid cyclic alkylester, (meth) acrylic-acid arylester, unsaturated dicarboxylic acid diester, ratio Cyclounsaturated compounds, 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, α-methyl styrene, acetoxy styrene, methoxy styrene, ethoxy styrene, chloro styrene, methyl vinyl benzoate, ethyl vinyl benzoate, 4-hydroxy Benzoic acid (3-methacryloyloxypropyl) ester, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, tert (meth) acrylic acid Structural units of butyl, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, glycidyl methacrylate, acrylonitrile, and the like Can be mentioned. In addition, Paragraph 0021 of Unexamined-Japanese-Patent No. 2004-264623-the compound of 0024 can be mentioned.

Above all, derived from other monomers having a group reacting with a repeating unit (a2) derived from a monomer or a crosslinking agent (in the present invention, (C) methylol crosslinking agent or (F) epoxy resin) derived from a monomer by (final) heating treatment. The repeating unit (a3) is preferable from the viewpoint of film strength. In the (final) heating treatment, the repeating unit (a3) derived from the monomer or the repeating unit (a3) derived from another monomer having a group reacting with a crosslinking agent added separately is a repeating unit derived from a monomer having a carboxyl group protected by acetal or ketal. Or a repeating unit derived from a monomer having a phenolic hydroxyl group protected by other than acetal or ketal. Moreover, it is preferable that it is a repeating unit derived from the monomer which has a carboxyl group protected by other than acetal or ketal. Specifically, (meth) acrylic acid tertiary alkyl ester is preferable, (meth) acrylic acid tert-butyl and (meth) acrylic acid 2-hydroxyethyl are more preferable, and methacrylic acid 2-hydroxyethyl, that is, HEMA Particularly preferred. Total of the said polymer (A ') and the polymer (A') of the repeating unit (a2) derived from a monomer by the said (final) heating process, or the repeating unit (a3) derived from the other monomer which has group reacting with the crosslinking agent of a separate addition. Or it is preferable that the ratio with respect to a polymer (A) is 1-50 mol%, It is more preferable that it is 5-40 mol%, It is especially preferable that it is 10-30 mol%.

In addition, the said (A) polymer adds the repeating unit derived from the monomer which has an unprotected carboxyl group, or the repeating unit derived from the monomer which has an unprotected phenolic hydroxyl group to the said polymer (A ') and a polymer (A'). Or it is preferable to contain 1-50 mol% with respect to a polymer (A) from a viewpoint of a sensitivity, It is more preferable that it is 5-40 mol%, It is especially preferable that it is 10-30 mol%. As a repeating unit derived from the monomer which has the said unprotected carboxyl group, or the repeating unit derived from the monomer which has an unprotected carboxyl group or a phenolic hydroxyl group, the monomer which has a well-known acidic group is mentioned, Especially, (meth) acrylic acid is preferable. And methacrylic acid is more preferable.

The monomer used as the repeating unit (a3) derived from the said other monomer can be used individually or in combination of 2 or more types. In the present invention, a repeating unit derived from a monomer having a carboxyl group or a phenolic hydroxyl group protected by a monomer other than acetal or ketal as a repeating unit derived from the monomer (a3) and an unprotected carboxyl group or a phenolic hydroxyl group. It is preferable to include together.

In addition, you may mix and use two or more types of (A) polymers used by this invention. The amount of the polymer (A) to be used is preferably 40 to 99% by weight, more preferably 60 to 98% by weight, further preferably based on the total weight of the composition (except the solvent) of the composition used in the present invention. 80 to 98% by weight.

<< molecular weight of (A) polymer >>

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

<< (A) manufacturing method of polymer >>

Moreover, although various methods are known also about the synthesis | combining method of (A) component, For example, it contains the radically polymerizable monomer used in order to form the repeating unit derived from the monomer represented by the said (a1) and said (a2) at least. A radically polymerizable monomer mixture can be synthesize | combined by superposing | polymerizing using the radical polymerization initiator in the organic solvent.

<(B) Mine Generator>

The composition used by this invention contains the (B) oxime sulfonate type photo-acid generator. As a photo-acid generator (also called "(B) component") used by this invention, the compound which generate | occur | produces an acid in response to actinic light of wavelength 300nm or more, Preferably wavelength 300-450nm is preferable, but the chemical structure It is not limited. Moreover, if it is a compound which produces | generates an acid in response to actinic light of wavelength 300nm or more by using together with a sensitizer also about the photo-acid generator which does not directly react to actinic light of wavelength 300nm or more, it can be used conveniently. As the photoacid generator used in the present invention, a photoacid generator for generating an acid having a pKa of 4 or less is preferable, and a photoacid generator for generating an acid having a pKa of 3 or less is more preferable.

(B) As an oxime sulfonate system photoacid generator, the compound containing the oxime sulfonate structure represented by the following general formula (B1) can be illustrated preferably.

General formula (B1)

[In formula (B1), R ²¹ represents an alkyl group or an aryl group.]

All the groups may be substituted, and the alkyl group in R ²¹ may be linear, branched or cyclic. Acceptable substituents are described below.

As an alkyl group of R <^21> , a C1-C10 linear or branched alkyl group is preferable. The alkyl group of R ²¹ includes a C6-C11 aryl group, a C1-C10 alkoxy group, or a cyclic alkyl alicyclic group such as a cyclic alkyl group (7,7-dimethyl-2-oxo nobornyl group, preferably bicyclo Or an alkyl group).

As an aryl group of R <^21> , a C6-C11 aryl group is preferable and a phenyl group or a naphthyl group is more preferable. The aryl group of R ²¹ may be substituted with a lower alkyl group, an alkoxy group or a halogen atom.

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

[In formula (B2), R <^42> represents an alkyl group or an aryl group, X represents an alkyl group, an alkoxy group, or a halogen atom, m4 represents the integer of 0-3, and when m4 is 2 or 3, even if several X is the same, May be different]

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

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

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

m4 is preferably 0 or 1.

M4 is 1 in said general formula (B2), X is a methyl group, a substitution position of X is an ortho position, R <^42> is a C1-C10 linear alkyl group, 7,7- dimethyl- 2-oxo nobornyl methyl group Or a compound that is a p-toluyl group.

It is more preferable that the compound containing the oxime sulfonate structure represented by said general formula (B1) is an oxime sulfonate compound represented with the following general formula (B3).

[In formula (B3), R <^43> represents an alkyl group or an aryl group, X <^1> represents a halogen atom, a hydroxyl group, a C1-C4 alkyl group, a C1-C4 alkoxy group, a cyano group, or a nitro group, n4 is 0-5. Represents an integer of

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

As X <^{1>, a} C1-C5 alkoxy group is preferable and a methoxy group is more preferable.

As n4, 0-2 are preferable and 0-1 are especially preferable.

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

Specific examples of the preferred oxime sulfonate compound include the following compounds (i) to (iii), and one kind of single use or two or more types can be used in combination. Compound (i)-(iv) can be obtained as a commercial item. Moreover, it can also be used in combination with another kind of (B) photo-acid generator.

It is preferable that it is also a compound represented with the following general formula (OS-1) as a compound containing the oxime sulfonate structure represented by said general formula (B1).

R ¹⁰¹ in formula (OS-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 a heteroaryl group. . R ¹⁰² represents an alkyl group or an aryl group.

¹⁰¹ X ^{is - O -, - S -,} - NH -, - NR 105 -, - CH 2 -, - CR 106 H- or -CR ¹⁰⁵ R ¹⁰⁷ - represents a, R ¹⁰⁵ ~R ¹⁰⁷ is an alkyl group or an aryl group Indicates.

R ¹²¹ to R ¹²⁴ each represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amide group, a sulfo group, a cyano group or an aryl group. Two of R ¹²¹ to R ¹²⁴ may be bonded to each other to form a ring.

As R ¹²¹ to R ¹²⁴ , a hydrogen atom, a halogen atom and an alkyl group are preferable, and embodiments in which at least two of R ¹²¹ to R ^{1 24} are bonded to each other to form an aryl group are also preferable. Especially, embodiment in which R <^121> -R <^124> is all hydrogen atoms is preferable from a viewpoint of a sensitivity.

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

As for the compound represented by the said general formula (OS-1), it is more preferable that it is a compound represented with the following general formula (OS-2).

In said general formula (OS-2), R <^101> , R <^102> , R <^121> -R <^124> are synonymous with the thing in Formula (OS-1), respectively, and a preferable example is also the same.

Among these, embodiment in which R ^{101 in} the general formula (OS-1) and the general formula (OS-2) is a cyano group or an aryl group is more preferable, and is represented by the general formula (OS-2), and R ^{The embodiment where 101} is a cyano group, a phenyl group, or a naphthyl group is the most preferable.

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

Although the specific example (example compounds b-1 to b-34) of the compound represented by the said general 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, Ts represents a tosyl group, and 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.

In this invention, as a compound containing the oxime sulfonate structure represented by said general formula (B1), it is represented by the following general formula (OS-3), the following general formula (OS-4), or the following general formula (OS-5). It is preferable that it is an oxime sulfonate compound.

R ²² , R ²⁵ and R ²⁸ in the formulas (OS-3) to (OS-5) each represent an alkyl group, an aryl group or a heteroaryl group, and R ²³ , R ²⁶ and R ²⁹ each represent a hydrogen atom, An alkyl group, an aryl group, or a halogen atom, R ²⁴ , R ²⁷ and R ³⁰ each represent a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group, and X ^{1 to} X ³ each represent oxygen An atom or a sulfur atom, n1 to n3 each represent 1 or 2, and m1 to m3 each represent an integer of 0 to 6;

The alkyl group, aryl group or heteroaryl group in R ²² , R ²⁵ and R ²⁸ in General Formulas (OS-3) to (OS-5) may have a substituent.

It is preferable that it is a C1-C30 alkyl group which may have a substituent as an alkyl group in R <^22> , R <^25> and R <^28> in said Formula (OS-3)-(OS-5).

As an alkyl group in R <^22> , R <^25> and R <^28> , 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-hex The group, n-octyl group, n-decyl group, n-dodecyl group, trifluoromethyl group, perfluoropropyl group, perfluorohexyl group, and benzyl group are preferable.

Examples of the substituent which the alkyl group in R ²² , R ^25, and R ²⁸ may have include a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, and an aminocarbonyl group. have.

Moreover, as said aryl group in R <^22> , R <^25> and R <^28> in the said general formula (OS-3)-(OS-5), the C6-C30 aryl group which may have a substituent is preferable.

As an aryl group in R <^22> , R <^25> and R <^28> , a phenyl group, p-methylphenyl group, p-chlorophenyl group, pentachlorophenyl group, pentafluorophenyl group, o-methoxyphenyl group, and p-phenoxyphenyl group are preferable.

Examples of the substituent which the aryl group in R ²² , R ²⁵ and R ²⁸ 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, And sulfonic acid groups, aminosulfonyl groups, and alkoxysulfonyl groups.

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

At least one ring may be a heteroaromatic ring in the heteroaryl group in R ²² , R ²⁵ and R ²⁸ in the general formulas (OS-3) to (OS-5), for example, even if the heteroaromatic ring and the benzene ring are condensed. good.

As a heteroaryl group in R ²² , R ²⁵ and R ²⁸ , 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 ring selected from the group which consists of these is mentioned.

Examples of the substituent that the heteroaryl group in R ²² , R ²⁵ and R ²⁸ may have include a halogen atom, an alkyl group, an alkyloxy group, an aryloxy group, an alkylthio group, an allylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, and an aminocarbonyl group. , Sulfonic acid group, aminosulfonyl group and alkoxysulfonyl group.

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

It is preferable that one or two of R ²³ , R ²⁶ and R ²⁹ present in two or more of the compounds in the general formulas (OS-3) to (OS-5) are alkyl groups, aryl groups or halogen atoms, and one is an alkyl group. It is more preferable that it is an aryl group or a halogen atom, It is especially preferable that one is an alkyl group and the remainder is a hydrogen atom.

The alkyl group or aryl group in R ²³ , R ²⁶ and R ²⁹ in General Formulas (OS-3) to (OS-5) may have a substituent. Here, as a substituent which the alkyl group or the aryl group in R <^23> , R <^26> and R <^29> may have, the group similar to the substituent which the alkyl group or the aryl group in said R <^22> , R <^25> and R <^28> may have can be illustrated.

As an alkyl group in R <^23> , R <^26> and R <^29> , 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.

As an alkyl group in R <^23> , R <^26> and R <^29> , a methyl group, an 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 are preferable, and methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, n-hexyl group A methyl group, an ethyl group, n-propyl group, n-butyl group, and n-hexyl group are more preferable, and a methyl group is preferable.

As an aryl group in R <^23> , R <^26> and R <^29> , it is preferable that they are a C6-C30 aryl group which may have a substituent.

As an aryl group in R <^23> , R <^26> and R <^29> , a phenyl group, p-methylphenyl group, o-chlorophenyl group, p-chlorophenyl group, o-methoxyphenyl group, and p-phenoxyphenyl group are specifically, preferable.

As a halogen atom in R <^23> , R <^26> and R <^29> , a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned.

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

In the general formulas (OS-3) to (OS-5), X ¹ to X ³ each represent O or S, and are preferably O.

In General Formulas (OS-3) to (OS-5), the ring containing X ¹ to X ³ as a reduction is a 5-membered ring or a 6-membered ring.

In the general formulas (OS-3) to (OS-5), n ^{1 to} n ³ each represent 1 or 2, and when X ^{1 to} X ³ are O, each of n ^{1 to} n ³ is preferably 1, Moreover, when X <^1> -X <^3> is S, it is preferable that n <^1> -n <^3> is 2, respectively.

In the general formulas (OS-3) to (OS-5), R ²⁴ , R ²⁷ and R ³⁰ each represent a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group. Especially, it is preferable that R <^24> , R <^27> and R <^30> are an alkyl group or an alkyloxy group, respectively.

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

It is preferable that it is a C1-C30 alkyl group which may have a substituent as said alkyl group in R <^24> , R <^27> and R <^30> in the said general formula (OS-3)-(OS-5).

As an alkyl group in R <^24> , R <^27> and R <^30> , 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-hex The group, n-octyl group, n-decyl group, n-dodecyl group, trifluoromethyl group, perfluoropropyl group, perfluorohexyl group, and benzyl group are preferable.

Examples of the substituent that the alkyl group in R ²⁴ , R ²⁷ and R ³⁰ may have include a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an allylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, and an aminocarbonyl group. have.

As said alkyloxy group in R <^24> , R <^27> and R <^30> in the said general formula (OS-3)-(OS-5), it is preferable that it is the alkyloxy group of 1-30 total carbons which may have a substituent.

As an alkyloxy group in R <^24> , R <^27> and R <^30> , a methyloxy group, an ethyloxy group, a butyloxy group, a hexyloxy group, a phenoxyethyloxy group, a trichloromethyloxy group, or an ethoxyethyloxy group is preferable. .

Examples of the substituent which the alkyloxy group in R ²⁴ , R ²⁷ and R ³⁰ may have include a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an allylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, and an aminocarbonyl group. Can be.

As aminosulfonyl group in R <^24> , R <^27> and R <^30> in the said general formula (OS-3)-(OS-5), a methylaminosulfonyl group, a dimethylaminosulfonyl group, a phenylaminosulfonyl group, a methylphenylaminosulfonyl group, Amino sulfonyl group is mentioned.

As an alkoxysulfonyl group in R <^24> , R <^27> and R <^30> in the said general formula (OS-3)-(OS-5), a methoxysulfonyl group, an ethoxysulfonyl group, a propyloxysulfonyl group, butyloxysulfonyl The group can be mentioned.

Moreover, m < ¹ > -m <^3> shows the integer of 0-6 in said general formula (OS-3)-(OS-5), respectively, 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 zero.

Moreover, it is especially preferable that the compound containing the oxime sulfonate structure represented by said general formula (B1) is an oxime sulfonate compound represented by either of the following general formula (OS-6)-(OS-11). .

[In formula (OS-6)-(OS-11), R ³⁰¹ -R ³⁰⁶ represent an alkyl group, an aryl group, or a heteroaryl group, R ³⁰⁷ represents a hydrogen atom or a bromine atom, and R ³⁰⁸ to R ³¹⁰ , R ³¹³ , R ³¹⁶ and R ³¹⁸ each represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or a chlorophenyl group, and R ³¹¹ and R ³¹⁴ each represent hydrogen An atom, a halogen atom, a methyl group or a methoxy group, and R ³¹² , R ³¹⁵ , R ³¹⁷ and R ³¹⁹ each represent a hydrogen atom or a methyl group]

R ³⁰¹ to R ³⁰⁶ in Formulas (OS-6) to (OS-11) have the same definitions as R ²² , R ^25, and R ^{28 in} Formulas (OS-3) to (OS-5). The same applies to the preferred embodiment.

R ³⁰⁷ in General Formula (OS-6) represents a hydrogen atom or a bromine atom, and is preferably a hydrogen atom.

In the general formulas (OS-6) to (OS-11), R ³⁰⁸ to R ³¹⁰ , R ³¹³ , R ^316, and R ³¹⁸ each represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, and bro It represents a mother methyl group, a bromoethyl group, a methoxymethyl group, a phenyl group, or a chlorophenyl group, It is preferable that it is a C1-C8 alkyl group, a halogen atom, or a phenyl group, It is more preferable that it is a C1-C8 alkyl group, It is a C1-C6 It is more preferable that it is an alkyl group, and it is especially preferable that it is a methyl group.

R <^311> and R <^314> in the said general formula (OS-8) and the said general formula (OS-9) represent a hydrogen atom, a halogen atom, a methyl group, or a methoxy group, respectively, and it is preferable that they are a hydrogen atom.

R <^312> , R <^315> , R <^317> and R <^319> in said general formula (OS-8)-(OS-11) represent 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, the stereo structure (E, Z) of an oxime may be either, or a mixture may be sufficient.

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

In the composition to be used in the present invention, the photoacid generator (B) is preferably used in an amount of 0.1 to 10 parts by mass based on 100 parts by mass of the total resin component (preferably solid content, more preferably the polymer (A)). It is more preferable to use 0.5-10 mass parts.

<(C) solvent>

The composition used by this invention contains the (C) solvent. It is preferable that the composition used by this invention is prepared as the solution which melt | dissolved the said (A), (B) component which is an essential component, and arbitrary components mentioned later in the (C) solvent.

As the (C) solvent used in the composition used in the present invention, a known solvent can be used, and ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, and propylene glycol monoalkyl ethers , Propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, di Propylene glycol monoalkyl ether acetates, esters, ketones, amides, lactones and the like can be exemplified.

As a (C) solvent used for the composition used by this invention, for example

(1) ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether;

(2) ethylene glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene glycol dipropyl ether;

(3) ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, and ethylene glycol monobutyl ether acetate;

(4) propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether;

(5) propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol monomethyl ether and diethylene glycol monoethyl ether;

(6) propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate and propylene glycol monobutyl ether acetate;

(7) diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol ethyl methyl ether;

(8) diethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, and diethylene glycol monobutyl ether acetate;

(9) dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether and dipropylene glycol monobutyl ether;

(10) dipropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, and dipropylene glycol ethyl methyl ether;

(11) dipropylene glycol monoalkyl ether acetates such as dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monopropyl ether acetate, and dipropylene glycol monobutyl ether acetate;

(12) lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate, n-butyl lactate, isobutyl lactate, n-amyl lactate, and isoamyl lactate;

(13) n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, n-hexyl acetate, 2-ethylhexyl acetate, ethyl propionate, ethyl propionate n-propyl, propionic acid isopropyl, n-butyl propionate, propionic acid Aliphatic carboxylic acid esters such as isobutyl, methyl butyrate, ethyl butyrate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate and isobutyl butyrate;

(14) ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate, 3-methoxypropionate, 3-meth Ethyl oxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, 3 Other esters such as methyl-3-methoxybutylbutylate, methyl acetoacetate, ethyl acetoacetate, methyl pyruvate, ethyl pyruvate and the like;

(15) ketones such as methyl ethyl ketone, methyl propyl ketone, methyl-n-butyl ketone, methyl isobutyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, and cyclohexanone;

Amides such as N-methylformamide, N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, and N-methylpyrrolidone;

(17) Lactones, such as (gamma) -butyrolactone, etc. are mentioned.

In addition, benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, capric acid, caprylic acid, and Solvents, such as octanol, 1-nonal, benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate, and propylene carbonate, may also be added. These solvents can be used individually by 1 type or in mixture of 2 or more types. It is preferable to use together single 1 type or 2 types, and, as for the solvent which can be used for this invention, it is more preferable to use 2 types together, and propylene glycol monoalkyl ether acetates or dialkyl ethers, diacetates, and diethylene It is more preferable to use glycol dialkyl ether or ester and butylene glycol alkyl ether acetate together.

Moreover, as a component (C), it is preferable that they are a boiling point of 130 degreeC or more, a solvent below 160 degreeC, a solvent with a boiling point of 160 degreeC or more, or a mixture thereof, a solvent with a boiling point of 130 degreeC or more and less than 160 degreeC, a solvent with a boiling point of 160 degreeC or more and 200 degrees C or less. Or it is more preferable that it is a mixture of these, It is further more preferable that it is a mixture of the boiling point of 130 degreeC or more and the solvent below 160 degreeC, and the solvent of boiling point 160 degreeC or more and 200 degrees C or less.

As a solvent of boiling point 130 degreeC or more and less than 160 degreeC, propylene glycol monomethyl ether acetate (boiling point 146 degreeC), propylene glycol monoethyl ether acetate (boiling point 158 degreeC), propylene glycol methyl- n-butyl ether (boiling point 155 degreeC), propylene glycol Methyl-n-propyl ether (boiling point of 131 degreeC) can be illustrated.

As a solvent of boiling point 160 degreeC or more, 3-ethoxy propionate ethyl (boiling point 170 degreeC), diethylene glycol methyl ethyl ether (boiling point 176 degreeC), propylene glycol monomethyl ether propionate (boiling point 160 degreeC), dipropylene glycol methyl ether acetate (Boiling point 213 ° C), 3-methoxybutyl ether acetate (boiling point 171 ° C), diethylene glycol diethyl ether (boiling point 189 ° C), diethylene glycol dimethyl ether (boiling point 162 ° C), propylene glycol diacetate (boiling point 190 ° C ), Diethylene glycol monoethyl ether acetate (boiling point 220 ° C.), dipropylene glycol dimethyl ether (boiling point 175 ° C.), and 1,3-butylene glycol diacetate (boiling point 232 ° C.) can be exemplified.

It is preferable that content of the (C) solvent in the composition used by this invention is 50-3,000 mass parts per 100 mass parts of all the resin components (preferably solid content, More preferably, the said (A) polymer) in a composition, 100 It is more preferable that it is -2,000 mass parts, and it is still more preferable that it is 150-1,500 mass parts.

<Other Ingredients>

In addition to the above, a sensitizer, an epoxy resin, an adhesion improving agent, a basic compound, and surfactant can be added to the composition used by this invention as needed. Moreover, well-known additives, such as a plasticizer, a thermal radical generator, antioxidant, a thermal acid generator, a ultraviolet absorber, a thickener, and organic or inorganic precipitation inhibitor, can be added to the composition used by this invention.

[Sensitizer]

It is preferable that the composition used by this invention contains a sensitizer in order to accelerate the decomposition | disassembly in combination with (B) photo-acid generator. A sensitizer absorbs actinic light and becomes an electron excited state. A sensitizer which has become an electron excited state comes into contact with a photoacid generator to generate an electron transfer, energy transfer, and heat generation. As a result, the photoacid generator causes a chemical change to decompose to produce an 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 (e.g., pyrene, perylene, triphenylene, anthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 3,7-dimethoxyanthracene, 9,10-dipropyloxy Anthracene), xanthenes (e.g., fluorescein, eosin, erythrosine, rhodamine B, rose bengal), xanthones (e.g., xanthone, thioxanthone, dimethyl thioxanthone, diethylthioke) Santon), cyanines (e.g., thiacarbocyanine, oxacarbocyanine), merocyanines (e.g., merocyanine, carbomerocyanine), rhodayanine, oxonol, thia Binary acids (e.g. thionine, methylene blue, toluidine blue), acridines (e.g. acridine orange, chloroprabin, acriprabin), acridones (e.g. acridon, 10-butyl-2-chloroacridone), anthraquinones (eg anthraquinones), squaryliums (eg squarylium), styryls, bases Styryls (eg 2- [2- [4- (dimethylamino) phenyl] ethenyl] benzoxazole), coumarins (eg 7-diethylamino4-methylcoumarin, 7-hydroxy 4-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.

[Epoxy resin]

The composition used by this invention may contain the epoxy resin as a crosslinking agent as needed. As said epoxy resin, the compound which has two or more epoxy groups can be added, for example in the molecule | numerator demonstrated below. By adding an epoxy resin, since it can be set as a harder cured film at the time of thermosetting, solvent resistance improves. As an epoxy resin, 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 (manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON860, EPICLON1050, EPICLON1055 (more than DICICON1055) As a bisphenol F type epoxy resin, JER806, JER807, JER4004, JER4005, JER4007, JER4010 (above Japan epoxy resin Co., Ltd.), EPICLON830, EPICLON835 (above DIC Corporation), LCE- 21, RE-602S (above Nippon Kayaku Co., Ltd.) are JER152, JER154, JER157S65, JER157S70 (above Japan epoxy resin Co., Ltd. product), EPICLON N-740, EPICLON N as phenol novolak-type epoxy resins -740, EPICLON N-770, EPICLON N-775 (above made by DIC Corporation), etc., are EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695 (manufactured by DIC Corporation), EOCN-1020 (manufactured by Nippon Kayaku Co., Ltd.) are ADEKA RESIN EP-4080S, copper EP-40 85S, copper EP-4088S (above made by ADEKA), Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, EHPE3150, EPOLEAD PB 3600, Copper PB 4700 (above Daicel Kagaku Kogyo Co., Ltd.) 1) etc. can be mentioned. In addition, ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4011S (above made by ADEKA), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501 And EPPN-502 (manufactured by ADEKA Co., Ltd.). 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, and a phenol novolak-type epoxy resin is more preferable.

[Contact improver]

The composition used by this invention may contain an adhesion improving agent. The adhesion improving agent which can be used for the composition used by this invention is a compound which improves the adhesiveness of the inorganic substance used as a base material, for example, silicon compounds, such as silicon, silicon oxide, and silicon nitride, metal, such as gold, copper, aluminum, and an insulating film. . Specifically, a silane coupling agent, a thiol type compound, etc. are mentioned. The silane coupling agent as the adhesion improving agent used in the present invention is intended to modify the interface, and any known one can be used without particular limitation.

As a preferable silane coupling agent, (gamma) -aminopropyl trimethoxysilane, (gamma) -aminopropyl triethoxysilane, (gamma)-glycidoxy propyltrialkoxy silane, (gamma)-glycidoxy propyl alkyl dialkoxysilane, (gamma)-meta Cryloxypropyl trialkoxysilane, (gamma)-methacryloxypropyl alkyl dialkoxysilane, (gamma)-chloropropyl trialkoxysilane, (gamma)-mercaptopropyl trialkoxysilane, (beta)-(3, 4- epoxycyclohexyl) ethyltrialkoxysilane And vinyltrialkoxysilane. Among these, γ-glycidoxypropyltrialkoxysilane and γ-methacryloxypropyltrialkoxysilane are more preferable, γ-glycidoxypropyltrialkoxysilane is more preferable, and 3-glycidoxypropyltrimethoxysilane Even more preferred. These may be used alone or in combination of two or more. They are effective for improving the adhesiveness with a board | substrate and also for adjusting the taper angle with a board | substrate.

0.1-20 mass parts is preferable with respect to 100 mass parts of all the resin components (preferably solid content, More preferably, the said (A) polymer) in content, as for content of the adhesion improving agent in the composition used by this invention, 0.5- 10 mass parts is more preferable.

[Basic compound]

The composition used by this invention may contain a basic compound. As a basic compound, although it is used by chemically amplified resist, it can select arbitrarily from among them. For example, aliphatic amine, aromatic amine, heterocyclic amine, quaternary ammonium hydroxide, quaternary ammonium salt of carboxylic acid, etc. are mentioned.

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

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

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

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

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

Moreover, especially the composition used by this invention at least 1 sort (s) among the compound represented by the following general formula (a), the compound represented by the following general formula (b), and the compound represented by the following general formula (c) is preferable, and The compound represented by formula (a) is more preferable. The effect of this invention is remarkably exhibited by using the compound represented by general formula (a).

Formula (a)

[In General Formula (a), R <^2> represents the linear or branched alkyl group which may have a C1-C6 substituent, or the cyclic alkyl group which may have a C3-C10 substituent. X represents an oxygen atom or a sulfur atom. Y ¹ represents an oxygen atom or an -NH- group. p1 represents an integer of 1 to 3]

Formula (b)

[In formula (b), R <^8> , R <^9> , R <^10> is a hydrogen atom, the linear or branched alkyl group which may have a C1-C6 substituent, the aryl group which may have a substituent, or a C3-C10 substituent, respectively. Represents a cyclic alkyl group which may have

General formula (c)

The compound represented by the general formula (a) preferably has a partial structure represented by a thiourea compound represented by the following general formula (c), wherein X is a sulfur atom from the viewpoint of the exposure margin. Do.

General formula (c)

[In general formula (c), R <^3> represents a C1-C6 linear or branched alkyl group or a C3-C10 cyclic alkyl group. Y ² represents an oxygen atom or an —NH— group. p2 represents an integer of 1 to 3]

(C) It is more preferable that a basic compound is also a thiourea compound represented by the following general formula (e), ie, it contains a morpholino group.

Formula (e)

[In general formula (e), R <^4> represents a C1-C6 linear or branched alkyl group or a C3-C10 cyclic alkyl group. p3 represents an integer of 1 to 3]

As a C1-C6 linear or branched alkyl group in R <^2> -R <^4> of the compound represented by said general formula (a), (d), (e), a methyl group, an ethyl group, a propyl group, n-butyl group C1-C4 alkyl groups, such as a sec-butyl group and a tert- butyl group, are preferable, A linear C1-C4 alkyl group is more preferable, A methyl group is especially preferable.

As a C3-C10 cyclic alkyl group in R <^2> -R <^4> of the compound represented by said general formula (a), (d), (e), it is a cyclopropyl group, a cyclobutyl group, a cyclohexyl group, an adamant C3-C10 cycloalkyl groups, such as a methyl group, are preferable, a C5-C10 cycloalkyl group is more preferable, and a cyclohexyl group is especially preferable.

Although the compound shown below is mentioned as a specific example of the basic compound represented by the said General formula (a), This invention is not limited to these.

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

It is preferable that content of the basic compound in the composition used by this invention is 0.001-1 mass part with respect to 100 mass parts of all resin components (preferably solid content, More preferably, the said (A) polymer) in a composition, 0.005 It is more preferable that it is -0.2 mass part.

[Surfactants]

The composition used by this invention may contain surfactant. As the surfactant, any of anionic, cationic, nonionic or zwitterionic can be used, but the preferred surfactant is a nonionic surfactant.

Examples of the nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkylphenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone and fluorine-based surfactants. In addition, KP (made by Shin-Etsu Chemical Co., Ltd.), polyflow (made by Kyoeisha Kagaku Co., Ltd.), F-top (made by JEMCO Corporation), mega pack (made by DIC Corporation), flu Each series, such as lard (made by Sumitomo 3M Co., Ltd.), Asahi Guard, a suffron (made by Asahi Glass Co., Ltd.), and PolyFox (made by OMNOVA), is mentioned.

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

In general formula (1)

[In formula (1), R ⁴⁰¹ and R ⁴⁰³ each represent a hydrogen atom or a methyl group, R ⁴⁰² represents a C1 or more linear alkylene group having 1 or more carbon atoms, and R ⁴⁰⁴ represents a hydrogen atom or 1 or more carbon atoms or less Represents an alkyl group, L represents an alkylene group of 3 to 6 carbon atoms, p and q are weight percentages representing the polymerization ratio, p represents a numerical value of 10 mass% or more and 80 mass% or less, and q is A numerical value of 20 mass% or more and 90 mass% or less, r represents an integer of 1 or more and 18 or less, and s represents an integer of 1 or more and 10 or less]

It is preferable that said L is a branched alkylene group represented by following General formula (2). R ⁴⁰⁵ in the general formula (2) represents an alkyl group having 1 to 4 carbon atoms, and in view of compatibility and wettability to the surface to be coated, an alkyl group having 1 to 3 carbon atoms is preferable, and has 2 or more carbon atoms. Three alkyl groups are more preferable. It is preferable that the sum (p + q) of p and q is p + q = 100, ie, 100 mass%.

General formula (2)

As for the weight average molecular weight (Mw) of the said polymer, 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 surfactant in the composition used by this invention is 10 mass parts or less with respect to 100 mass parts of all the resin components (preferably solid content, More preferably, the said (A) polymer) in a composition, 0.01- It is more preferable that it is 10 mass parts, and it is still more preferable that it is 0.01-1 mass part.

[Antioxidant]

The composition used by 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, saccharides, nitrites, sulfites, tyionates, and hydroxylamines. Derivatives; and the like. Among these, a phenolic antioxidant is especially preferable from a viewpoint of coloring of a cured film and reduction of a film thickness. 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, adecastabu AO-60, adecastaab AO-80 (made by ADEKA Corporation), and Irganox 1098 (made by Chiba Japan Co., Ltd.) are mentioned, for example.

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

Moreover, you may add the various ultraviolet absorbers, metal inactivating agents, etc. which were described in "New development of polymer additives" (Daily Industry Co., Ltd.) as additives other than antioxidant to the composition used by this invention.

[Method of Preparation of Composition]

The essential components of (A) and (B) of the above-mentioned composition are mixed in a predetermined ratio and by any method, stirred and dissolved to prepare a composition for use in the present invention. For example, after making (A) and (B) components into the solution which melt | dissolved in the (C) solvent previously, respectively, these can also be mixed in a predetermined ratio, and the resin composition can also be prepared. The composition solution prepared as mentioned above can also be used for use, after filtering using a filter etc. of 0.2 micrometer of pore diameters.

(2) removing the solvent from the applied composition

In the process of removing the solvent of (2), a solvent is removed from the apply | coated film | membrane by reduced pressure (vacuum) and / or heating, and a dry coating film is formed on a board | substrate.

The desired dry coating film can be formed by apply | coating the composition used by this invention 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 in which the black matrix layer and the color filter layer were further formed as needed, and the transparent conductive circuit layer was further formed can be illustrated. Although there is no restriction | limiting in particular as a method of apply | coating a composition to a board | substrate, Especially, in this invention, it is preferable to apply a composition to a board | substrate. The coating method to a board | substrate is not specifically limited, For example, methods, such as a slit coat method, a spray method, a roll coat method, and a spin coating method, can be used. Among them, the slit coat method is preferable from the viewpoint of being suitable for large substrates. The production of a large substrate is preferable because of its high productivity. Here, a large board | substrate means the board | substrate of the magnitude | size whose each side is 1 m or more.

In addition, the heating conditions of (2) solvent removal process are a range in which an acid-decomposable group decomposes in the repeating unit (a1) derived from the monomer in (A) component in an unexposed part, and (A) component is not made soluble in an alkaline developing solution. Although it changes also with kinds and compounding ratio of each component, Preferably it is about 30 to 120 second at 80-130 degreeC.

In this invention, you may perform prebaking before an exposure process. By prebaking, the effect of the present invention tends to be more effectively exerted. It is preferable to perform prebaking at 70-120 degreeC, and it is more preferable to carry out at 80-110 degreeC. In addition, it is preferable to carry out prebaking for 0.5 to 5 minutes, and it is more preferable to carry out for 1 to 3 minutes.

(3) Process of irradiating actinic light to composition by microlens array exposure machine

In an exposure process, actinic light is irradiated to the board | substrate which formed the coating film through the mask which has a predetermined | prescribed pattern. After the exposure step, heat treatment (PEB) is performed as necessary, and then in the developing step, the exposure area is removed using an alkaline developer to form an image pattern.

In an exposure process, actinic light is irradiated to the obtained coating film. In this step, (B) the photoacid generator decomposes and acid is generated. By the action of the generated acid, the acid decomposable group contained in the resin in which alkali solubility is increased by the action of the acid (A) is hydrolyzed to form a carboxyl group or a phenolic hydroxyl group.

As exposure time, 1 to 100 second is preferable and 5 to 60 second is more preferable. By exposing on such conditions, the effect of this invention is exhibited more effectively.

As the exposure method, MLA exposure is employed in the present invention. The MLA exposure method is an exposure method that employs an optical system in which microlenses are arranged in a lattice form, and is an exposure apparatus that can cope with ultra high-definition display manufacture in a smartphone, a tablet PC, and the like. 1-1000 micrometers is preferable and, as for the diameter of a micro lens, 10-500 micrometers is more preferable. The micro lens is preferably convex. Each lens is preferably arranged at a pitch of 10 to 300 mu m. It is preferable that projection magnification is 1: 1 normally.

As a specific exposure apparatus, what was described in Unexamined-Japanese-Patent No. 2011-118155 is mentioned, The content of Unexamined-Japanese-Patent No. 2011-118155 is contained in this specification. That is, a photomask having a mask pattern having the same shape as the exposure pattern exposed on the surface of the object to be held on the stage, and the mask pattern disposed between the photomask and the stage and formed on the photomask. A plurality of unit lens groups formed by arranging a plurality of convex lenses in the normal direction of the photomask so that granular images can be imaged on the surface of the exposed object are arranged in plural in a plane parallel to the surface of the exposed object held on the photomask and the stage. An exposure apparatus can be adopted, comprising a lens assembly and moving means for moving the lens assembly in the plane parallel to the surface of the object to be exposed on the photomask and the stage. Moreover, the MLA exposure apparatus etc. which are sold from V Technologies, Inc. can also be employ | adopted suitably.

As an exposure light source by actinic light, a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a chemical lamp, an LED light source, an excimer laser generator, etc. can be used. As the actinic ray, actinic rays having a wavelength of 300 nm or more and 450 nm or less, such as g-ray (436 nm), i-ray (365 nm) and h-ray (405 nm), can be preferably used. Moreover, irradiation light can also be adjusted through spectroscopic filters, such as a long wavelength cut filter, a short wavelength cut filter, and a bandpass filter, as needed.

Post-exposure heat treatment: Post Exposure Bake (hereinafter also referred to as "PEB") is performed to accelerate the hydrolysis reaction in the region where the acid catalyst is generated. PEB can promote the production of carboxyl groups or phenolic hydroxyl groups from acid-decomposable groups. 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 100 degrees C or less are especially preferable. 0.5-5 minutes are preferable and, as for the time of PEB, 1-3 minutes are more preferable. By carrying out PEB under these conditions, the effect of the present invention is more effectively exerted.

The acid-decomposable group in the repeating unit derived from the monomer represented by the above-mentioned 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 group or Since a phenolic hydroxyl group is generated, a positive image may be formed by development without necessarily performing PEB, but in the production method of the present invention, curing obtained by performing the postbaking step (5) using the composition used in the present invention The membrane can reduce the heat flow. Therefore, when the cured film obtained by the manufacturing method of the cured film of this invention is used, for example as a resist for a board | substrate, even if the cured film of the board | substrate this invention was heated, the resolution of a pattern will not deteriorate for the most part. In addition, in this specification, the term "thermal flow" is deformed when the cross-sectional shape of the pattern cured film formed by the exposure and development processes is heated when the cured film is heated (preferably 180 ° C or more, more preferably 200 ° C to 240 ° C). , Taper angle, etc. are deteriorated.

(4) Process of developing with aqueous developer

In the developing step of (4), the polymer having a free carboxyl group or phenolic hydroxyl group is developed with an aqueous developer. The aqueous developer is preferably 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.

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; An aqueous solution of sodium silicate, sodium metasilicate or the like can be used. Moreover, the aqueous solution which added an appropriate amount of water-soluble organic solvents, such as methanol and ethanol, and surfactant to the aqueous solution of the said alkalis can also be used as a developing solution.

The pH of the 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 puddle method and a dipping method. After development, flowing water can be washed for 30 to 90 seconds to form a desired pattern.

20-30 degreeC is preferable and, as for the temperature of a developing solution, 20-25 degreeC is more preferable.

The development may be performed by shower development or puddle development. As for the nozzle pressure of the shower at this time, 0.01-0.2 Mpa is preferable.

In this invention, it is also preferable to perform a rinsing process after a image development process. It is preferable to perform a rinse process with a rinse liquid (preferably pure water). The rinsing treatment may also be performed by a shower, and in this case, the pressure of the nozzle is preferably 0.01 to 0.2 MPa. 20-30 degreeC is preferable and, as for the temperature of a rinsing process, 20-25 degreeC is more preferable. 10 to 180 second is preferable and, as for the time of a rinsing process, 10 to 60 second is more preferable. By performing the rinsing treatment, the residue is more effectively removed, and the effect of the present invention is more effectively exhibited.

(5) postbaking process

By heating the positive image obtained in the post-baking process of (5), the acid-decomposable group in the repeating unit (a1) derived from a monomer is thermally decomposed to produce a carboxyl group or a phenolic hydroxyl group, and the crosslinking group of the repeating unit (a2) derived from a monomer, and A cured film can be formed by crosslinking the partial structure represented by the said General formula (c1) with the methylol crosslinking agent which has at least 1 in a molecule | numerator.

The composition used by this invention contains the methylol crosslinking agent which has at least 1 partial structure represented by the said General formula (c1) in a molecule | numerator, storage stability, sensitivity solvent resistance, and the resolution after the post-baking process after a developing process. This is excellent. By using the composition used by this invention, the manufacturing method of the cured film of this invention can raise crosslinking property more than when crosslinking only by the crosslinking group of the repeating unit (a2) derived from a monomer in the postbaking process of (5). have.

It is preferable to heat this heating to high temperature 150 degreeC or more, It is more preferable to heat to 180-250 degreeC, It is especially preferable to heat to 200-240 degreeC. Although heating time can be set suitably according to heating temperature etc., it is preferable to set it in the range of 10 to 90 minutes.

The addition of a step of totally irradiating actinic light, preferably ultraviolet rays, to the development pattern before the postbaking process may promote the crosslinking reaction by the acid generated by actinic light irradiation.

For a pattern corresponding to an unexposed area obtained by development, using a heating device such as a hot plate or an oven, for a predetermined time, for example, at a temperature of 180 to 250 ° C. for a predetermined time, for example, 5 to 60 minutes. In an oven, the acid-decomposable group in component (A) is decomposed by heat treatment for 30 to 90 minutes to generate a carboxyl group or a phenolic hydroxyl group, and a crosslinkable group in the repeating unit (a2) derived from the monomer, and the general formula (c1). By reacting and crosslinking the partial structure shown with the methylol crosslinking agent which has at least one in a molecule | numerator, a protective film and an interlayer insulation film excellent in heat resistance, hardness, etc. 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, the substrate having the pattern is re-exposed by actinic light and then postbaked (re-exposure / post-baking) to generate an acid from component (B) present in the unexposed portion, thereby accelerating the crosslinking process. It is preferable to function as a catalyst.

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, it is preferable to perform whole surface exposure to the side in which the film | membrane was formed with the composition used by this invention of a board | substrate in the said re-exposure process.

As a preferable exposure amount of a re-exposure process, it is 100-1,000mJ / cm <2>.

[Curing film]

The cured film (interlayer insulation film) in this invention can be formed by the manufacturing method of the said interlayer insulation film. By the composition used by this invention, the interlayer insulation film which is excellent in insulation and has high transparency also when baked at high temperature is obtained. Since the interlayer insulation film of this invention has high transparency and excellent cured film physical property, it is useful for the use of a display apparatus (especially an organic electroluminescence display or a liquid crystal display device).

[2nd Embodiment of the manufacturing method of the resin pattern]

Next, 2nd Embodiment of the manufacturing method of the resin pattern of this invention is described.

The manufacturing method of the resin pattern of this invention includes the process of (1)-(4) of the manufacturing method of the resin pattern mentioned above, for example, and the resin pattern formed (5) after the process of developing with said (4) aqueous developing solution. It is preferable to apply to the manufacturing method of a patterned substrate which further includes the process of etching the said board | substrate using a mask as a mask, and (6) the process of peeling the said resin pattern.

That is, it characterized by including the process of the following (1)-(6).

(1) process of apply | coating the composition used by this invention on a board | substrate,

(2) removing the solvent from the applied composition,

(3) exposing and irradiating actinic light using an MLA exposure machine;

(4) developing with an aqueous developer;

(5) a step of etching the substrate using the formed resin pattern as a mask, and

(6) Process of peeling the said resin pattern.

Each step will be described below in order.

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

[Composition]

The composition for exposing the microlens array of the present invention contains a resin (A) which increases alkali solubility under the action of an acid, (B) an oxime sulfonate-based photoacid generator, (C) a solvent, and (D) a basic compound, Moreover, it is preferable that it is a composition for etching resist uses used when exposing using a microlens array exposure machine. In particular, the composition used in the present invention is preferably used for a positive resist.

Hereinafter, these components are demonstrated.

(A) Resin whose alkali solubility is increased by the action of an acid

It is preferable that it is insoluble or poorly soluble with alkali, and resin which becomes alkali-soluble when the group protected by the action of an acid decomposes with resin which alkali solubility increases by the action of (A) acid used by this invention. It is preferable. In the present invention, "alkali solubility" and "alkali insolubility" are synonymous with the term in resin in which alkali solubility increases by the action of (A) acid described in 1st Embodiment of the manufacturing method of the resin pattern mentioned above. to be.

In the present invention, the resin in which alkali solubility is increased by the action of an acid is preferably a resin containing a repeating unit having a residue in which a carboxyl group is protected with an acid-decomposable group or a repeating unit having a residue in which a phenolic hydroxyl group is protected with an acid-decomposable group. It is preferable that it is more preferable that it is resin which a phenolic hydroxyl group contains the repeating unit which has the residue protected by the acid-decomposable group.

In this invention, it is preferable that the repeating unit which comprises (A) resin contains the repeating unit containing an aromatic ring, and it is more preferable that the repeating unit containing a benzene ring is included. Moreover, as for (A) resin, it is more preferable that a principal chain is a carbon-carbon bond, and a benzene ring is included in a side chain.

The 1st preferable embodiment of (A) resin used by this invention is resin containing the repeating unit of protected hydroxy styrene and the monomer unit of hydroxy styrene. Specifically, Paragraph No. 0098-0120 of Unexamined-Japanese-Patent No. 2003-162051, Paragraph No. 0074 of Unexamined-Japanese-Patent No. 2003-066611, and the resin of 0151 can be used.

The resin is preferably a resin containing a repeating unit represented by the following general formula (I) and a repeating unit represented by the following general formula (II).

In general formula (I)

[In General Formula (I), R is a residue in which a carboxyl group is protected by an acid-decomposable group or a phenolic hydroxyl group is protected by an acid-decomposable group, respectively. Ra ⁷ is a hydrogen atom or a methyl group, and Ra ⁸ is a halogen atom, a hydroxyl group or an alkyl group having 1 to 3 carbon atoms. n1 is an integer of 0 to 4]

In the above formula, the OR group is preferably bonded to the para position.

General formula (Ⅱ)

[In general formula (II), Ra <^9> is a hydrogen atom or a methyl group, Ra <^10> is a halogen atom, a hydroxyl group, or a C1-C3 alkyl group. n2 is an integer of 0 to 4]

In the above formula, the OH group is preferably bonded to the para position.

Resin containing the repeating unit represented by the following general formula (I) and the repeating unit represented by the following general formula (II), Preferably it is represented by the repeating unit represented by the following general formula (III) and general formula (IV) Losing is a resin containing repeating structural units. Thereby, the effect of this invention becomes more remarkable.

In said general formula (III), L represents a hydrogen atom, the linear, branched or cyclic alkyl group which may be substituted, or the aralkyl group which may be substituted. Z represents a linear, branched or cyclic alkyl group which may be substituted or an aralkyl group which may be substituted. In addition, Z and L may combine to form a 5- or 6-membered ring.

Examples of the alkyl groups of L and Z in the general formula (III) include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, pentyl group, cyclopentyl group, hexyl group, C1-C20 linear, branched, or cyclic | annular things, such as a cyclohexyl group, an octyl group, and a dodecyl group, are mentioned.

As a preferable substituent which the alkyl group of L and Z in the said General formula (III) may have, an alkyl group, an alkoxy group, a hydroxyl group, a halogen atom, a nitro group, an acyl group, an acyloxy group, an acylamino group, a sulfonylamino group, and an alkyl tea Heterocyclic residues, such as a group, an arylthio group, an aralkylthio group, a thiophene carbonyloxy group, a thiophene methylcarbonyloxy group, and a pyrrolidone residue, etc. are mentioned, Preferably it is 12 or less carbon atoms.

As an alkyl group which has a substituent of L and Z in the said General formula (III), for example, a cyclohexylethyl group, an alkylcarbonyloxymethyl group, an alkylcarbonyloxyethyl group, an arylcarbonyloxyethyl group, an aralkylcarbonyloxyethyl group, Alkyloxymethyl group, aryloxymethyl group, aralkyloxymethyl group, alkyloxyethyl group, aryloxyethyl group, aralkyloxyethyl group, alkylthiomethyl group, arylthiomethyl group, aralkylthiomethyl group, alkylthioethyl group, arylthioethyl group, aralkylthio Ethyl group etc. are mentioned.

Although the alkyl group in the case where the substituent containing the alkyl group which has a substituent of L and Z in the said General formula (III) is an alkyl group is not specifically limited, Any of a linear, cyclic, or branched phase may be sufficient as mentioned above You may further have substituents, such as an alkyl group and an alkoxy group. Examples of the alkylcarbonyloxyethyl group include cyclohexylcarbonyloxyethyl group, t-butylcyclohexylcarbonyloxyethyl group, n-butylcyclohexylcarbonyloxyethyl group and the like.

Although the aryl group in the case where the substituent containing the alkyl group which has a substituent of L and Z in the said General formula (III) is an aryl group is not specifically limited, Generally, a phenyl group, xylyl group, toluyl group, cumenyl group, naphthyl group And C6-C14, such as anthracenyl group, You may further have substituents, such as an alkyl group and an alkoxy group mentioned above. Examples of the allyloxyethyl group include a phenyloxyethyl group, a cyclohexylphenyloxyethyl group, and the like. Although aralkyl is not specifically limited, Benzyl group etc. are mentioned, for example. Benzylcarbonyloxyethyl group etc. are mentioned as an example of the said aralkylcarbonyloxyethyl group.

As an aralkyl group of L and Z in the said General formula (III), C1-C15 things, such as a substituted or unsubstituted benzyl group and a substituted or unsubstituted phenethyl group, are mentioned, for example. Preferred substituents for the aralkyl group include an alkoxy group, hydroxyl group, halogen atom, nitro group, acyl group, acylamino group, sulfonylamino group, alkylthio group, arylthio group, aralkylthio group, and the like. Aralkyl group having a substituent As an alkoxy benzyl group, a hydroxybenzyl group, a phenylthio phenethyl group etc. are mentioned, for example. Preferably the range of carbon number of the substituent which an aralkyl group as L or Z may have is 12 or less.

As described above, when L and Z in the general formula (III) are a substituted alkyl group or a substituted aralkyl group, it is preferable to introduce a bulky group such as a phenyl group or a cyclohexyl group at the terminal thereof. .

The tetrahydropyran ring, the tetrahydrofuran ring, etc. are mentioned as a 5 or 6 membered ring which L and Z in the said General formula (III) couple | bond with each other, and form.

It is preferable that the substituent of the benzene ring in the repeating unit represented by general formula (III) and the repeating structural unit represented by general formula (IV) is couple | bonded with the para position.

Especially preferable embodiment of resin containing the repeating unit represented by the following general formula (I), and the repeating unit represented by the following general formula (II) is a repeating unit represented by the following general formula (V), and a general formula ( It is resin which has a repeating unit represented by VI).

In general formula (V)

[Ra ¹ to Ra ⁶ in General Formula (V) are each a hydrogen atom, an alkyl group which may have a substituent having 1 to 20 carbon atoms, or an aryl group which may have a substituent, and may be bonded to each other to form a ring. Ra ⁷ is a hydrogen atom or a methyl group, and Ra ⁸ is a halogen atom, a hydroxyl group or an alkyl group having 1 to 3 carbon atoms. n1 is an integer of 0 to 4]

Examples of the alkyl group in Ra ^{1 to} Ra ⁶ include a linear, branched, cyclic alkyl group and a phenyl group which may have a substituent, each having 1 to 20 carbon atoms, which may have a substituent. Linear, branched 3 to 12 carbon atoms or cyclic alkyl groups having 5 to 10 carbon atoms are preferable. Specific examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl, Ecosyl group, isopropyl group, isobutyl group, s-butyl group, tert-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group And a cyclohexyl group, a cyclopentyl group, and 2-norbornyl group.

A phenyl group and a naphthyl group are mentioned as a specific example of the aryl group in Ra <^1> -Ra <^6> .

Ra ^{1 to} Ra ⁶ are each preferably a hydrogen atom, a straight chain having 1 to 12 carbon atoms, a branched carbon group having 3 to 12 carbon atoms, or a cyclic alkyl group or a phenyl group having 5 to 10 carbon atoms, and a hydrogen atom and carbon More preferably, a linear alkyl group having 1 to 12 atoms or a phenyl group is more preferable, and a hydrogen atom, a methyl group, or a phenyl group is more preferable.

It is preferable that Ra <^1> , Ra <^2> , Ra <^3> , Ra <^5> is a hydrogen atom, Ra <^1> , Ra <^2> , Ra <^3> , Ra <^5> is a hydrogen atom, and it is more preferable that Ra <^4> and Ra <^6> are the said groups, respectively. .

Ra ⁷ is a hydrogen atom or a methyl group, and a hydrogen atom is preferable.

Ra <^8> is a halogen atom, a hydroxyl group, or a C1-C3 alkyl group, and a chlorine atom, a bromine atom, a hydroxyl group, or a methyl group is preferable.

n1 is an integer of 0-4, and 0 is preferable for n1.

General formula (VI)

[In general formula (VI), Ra <^9> is a hydrogen atom or a methyl group, Ra <^10> is a halogen atom, a hydroxyl group, or a C1-C3 alkyl group. n1 is an integer of 0 to 4]

Ra ⁹ is a hydrogen atom or a methyl group, and a hydrogen atom is preferable.

Ra ¹⁰ is a halogen atom, a hydroxyl group or an alkyl group having 1 to 3 carbon atoms, and a chlorine atom, bromine atom, hydroxyl group or methyl group is preferable.

n2 is an integer of 0-4, and 0 is preferable.

In this invention, as content of the repeating unit represented by general formula (I) (preferably general formula (III) or general formula (V)), 5-90 mol% is preferable with respect to all the repeating units, More preferably, Is 10-75 mol%, More preferably, it is 10-45 mol%. Moreover, as content of the repeating unit represented by general formula (II) (preferably general formula (IV) or general formula (V)), 5-95 mol% is preferable with respect to all the repeating units, More preferably, it is 10 It is -85 mol%.

It is preferable that the sum of the repeating unit represented by General formula (I) and the repeating unit represented by General formula (II) of the (A) resin used by this invention is 95 mol% or more of all the repeating units. Moreover, as for resin used by this invention, (A) resin whose polydispersity (weight average molecular weight / number average molecular weight) is larger than 2.0 is preferable. More preferably, it is 2.01-7.00, It is still more preferable that it is 2.01-5.00, It is especially preferable that it is 2.01-4.00. By setting the polydispersity to 7.00 or less, the resolution tends to be improved, and it is possible to more effectively suppress that the resist pattern becomes tapered. In addition, at 2.00 or less, resolution decreases or development residues occur. Here, a weight average molecular weight and a number average molecular weight are defined by the polystyrene conversion value of gel permeation chromatography.

Although the specific example of resin used preferably by 1st Embodiment below is shown in the following Example of this application, other following resin is illustrated. It goes without saying that the present invention is not limited to these.

In the above specific examples, Me represents a methyl group, Et represents an ethyl group, n-Bu represents an n-butyl group, iso-Bu represents an isobutyl group, and t-Bu represents a t-butyl group.

As a 2nd preferable embodiment of (A-1) resin used by this invention, the novolak resin obtained by protecting one or all the hydroxyl groups with the group which can be detach | desorbed by the effect | action of an acid is mentioned. Especially, the novolak resin in which one part or all hydroxyl group was protected by the acetal or ketal structure is preferable, and the novolak resin protected by the ethoxyethyl group is more preferable. As such a novolak resin, Paragraph No. 0007 of Unexamined-Japanese-Patent No. 2003-98671-description of 0018 can be considered into consideration. In the novolak resin, the repeating unit having a protected group is preferably from 5 to 90 mol%, more preferably from 10 to 75 mol%, still more preferably from 10 to 45 mol% based on the total repeating units.

It is preferable that the weight average molecular weights (Mw) of said (A) resin are 5,000-300,000, More preferably, it is 5,000-100,000, Most preferably, it is 5,000-60,000. By setting it as 5,000 or more, the film | membrane decrease by the phenomenon of an unexposed part can be suppressed, and by setting it as 300,000 or less, the melt | dissolution rate with respect to alkali of resin itself slows down, and it can suppress more effectively that a sensitivity falls. The weight average molecular weight here is defined by the polystyrene conversion value of gel permeation chromatography.

In addition, you may mix and use two or more types of (A) resin used by this invention. The amount of the resin (A) to be used is preferably 40 to 99% by weight, more preferably 60 to 98% by weight, still more preferably 80 to 98% by weight based on the total weight of the composition (excluding the solvent). to be.

The composition used by this invention is adjusted as a solution by melt | dissolving each said component in the solvent which melt | dissolves, for example, by filtering with a filter of about 0.05 micrometer-about 0.2 micrometer of pore diameters, for example. As a solvent used here, for example, ethylene glycol monoethyl ether acetate, cyclohexanone, 2-heptanone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, and propylene glycol monoethyl Ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl β-methoxyisobutyrate, ethyl butyrate, propyl butyrate, methylisobutyl ketone, ethyl acetate, isoamyl acetate, ethyl lactate, toluene, xylene, Cyclohexyl acetate, diacetone alcohol, N-methylpyrrolidone, N, N-dimethylformamide, γ-butyrolactone, N, N-dimethylacetamide, propylene carbonate, ethylene carbonate and the like. These solvents can be used individually or in combination. The choice of solvent is important because it affects the solubility of the positive photoresist composition of the present invention, the applicability to the substrate, the storage stability, and the like. In addition, since the moisture contained in the solvent affects the performance of the resist, the smaller one is preferable.

Moreover, it is preferable that the composition used by this invention reduces metal impurities, such as metal, and impurity components, such as a halogen ion, to 100 ppb or less. The presence of many of these impurities is not preferable because it may cause malfunctions, defects, and yield decrease in manufacturing a semiconductor device.

(B) mine generator

The composition used by this invention contains an oxime sulfonate-type acid generator. The oxime sulfonate acid generator used in the present invention has the same meaning as the oxime sulfonate acid generator described in the first embodiment of the method for producing a resin pattern described above, and the preferred range is also the same.

(C) solvent

The composition used by this invention contains the (C) solvent. It is preferable that the composition used by this invention is prepared as a solution which melt | dissolved arbitrary components in the (D) solvent in addition to (A) resin which is an essential component, (B) photo-acid generator, and (D) basic compound.

As (C) solvent used for the composition used by this invention, it is synonymous with the solvent described in 1st Embodiment of the manufacturing method of the resin pattern mentioned above, and its preferable range is also the same.

(D) basic compound

It is preferable that the composition used by this invention contains the (D) basic compound. The basic compound used by this invention is synonymous with the basic compound described in 1st Embodiment of the manufacturing method of the above-mentioned resin pattern.

In the present invention, the amount of the basic compound (D) added is usually based on the total resin component (preferably solid content, more preferably component (A)) in the composition from the viewpoint of satisfying the sensitivity resolution and the entire exposure margin. It is used in the range of 0.001 to 20% by weight, preferably 0.005 to 10% by weight, most preferably 0.01 to 5% by weight.

<Other Ingredients>

In the positive composition of the present invention, in addition to the component (A), the component (B), the component (C) and the component (D), (N) sensitizer, (G) adhesion improving agent, and (I) surfactant may be added as necessary. It may be preferably added. Moreover, well-known additives, such as a plasticizer, a thermal radical generator, antioxidant, a thermal acid generator, a ultraviolet absorber, a thickener, and organic or inorganic precipitation inhibitor, can be added to the positive composition of this invention.

(N) sensitizer

It is preferable that the composition used by this invention contains a sensitizer in order to accelerate the decomposition | disassembly in combination with (B) photo-acid generator. The sensitizer used by this invention is synonymous with the sensitizer described in 1st Embodiment of the manufacturing method of the above-mentioned resin pattern.

As for content of the (N) sensitizer in the composition used by this invention, 0.1-20 mass parts is preferable with respect to 100 mass parts of all the resin components (preferably solid content, more preferably said (A) resin) in a composition, 0.5-10 mass parts is more preferable.

(G) adhesion improver

The composition used by this invention may contain the (G) adhesion improving agent. The (G) adhesion improving agent which can be used for the composition used by this invention improves the adhesiveness of the inorganic substance used as a base material, for example, silicon compounds, such as silicon, silicon oxide, and silicon nitride, metals, such as gold, copper, aluminum, and an insulating film. It is a compound to make. Specifically, a silane coupling agent, a thiol type compound, etc. are mentioned. The silane coupling agent as a (G) adhesion improving agent used by this invention aims at the modification of an interface, A well-known thing can be used without a restriction | limiting in particular.

As a preferable silane coupling agent, (gamma) -aminopropyl trimethoxysilane, (gamma) -aminopropyl triethoxysilane, (gamma)-glycidoxy propyltrialkoxy silane, (gamma)-glycidoxy propyl alkyl dialkoxysilane, (gamma)-meta Cryloxypropyl trialkoxysilane, (gamma)-methacryloxypropyl alkyl dialkoxysilane, (gamma)-chloropropyl trialkoxysilane, (gamma)-mercaptopropyl trialkoxysilane, (beta)-(3, 4- epoxycyclohexyl) ethyltrialkoxysilane And vinyltrialkoxysilane. Among these, γ-glycidoxypropyltrialkoxysilane and γ-methacryloxypropyltrialkoxysilane are more preferable, γ-glycidoxypropyltrialkoxysilane is more preferable, and 3-glycidoxypropyltrimethoxysilane Even more preferred. These may be used alone or in combination of two or more. They are effective for improving the adhesiveness with a board | substrate and also for adjusting the taper angle with a board | substrate.

As for content of the (G) adhesion improving agent in the composition used by this invention, 0.1-20 mass parts is preferable with respect to 100 mass parts of all the resin components (preferably solid content, more preferably said (A) resin) in a composition, 0.5-10 mass parts is more preferable.

(I) surfactant

The composition used by this invention may contain surfactant (I). As (I) surfactant, it is synonymous with surfactant described in 1st Embodiment of the manufacturing method of the resin pattern mentioned above, and its preferable range is also the same.

[Antioxidant]

The composition used by this invention may contain antioxidant. As antioxidant, it is synonymous with antioxidant described in 1st Embodiment of the manufacturing method of the resin pattern mentioned above, and its preferable range is also the same.

[Method of Preparation of Composition]

The essential components of (A)-(D) of the above-mentioned composition are mixed by a predetermined ratio and by arbitrary methods, and are stirred and dissolved, and the composition used by this invention is prepared. For example, after making (A)-(C) component into the solution which melt | dissolved in the (D) solvent previously, respectively, these can also be mixed in a predetermined | prescribed ratio, and resin composition can also be prepared. The composition solution prepared as mentioned above can also be used for use, after filtering using a filter etc. of 0.2 micrometer of pore diameters.

(2) removing the solvent from the applied composition

In the solvent removal process of (2), the desired dry coating film can be formed by apply | coating the composition used by this invention to a predetermined board | substrate, and removing a solvent by pressure reduction and / or heating (prebaking). The said board | substrate, the method of apply | coating a composition to a board | substrate, and the coating method to a board | substrate are the same as that of 1st Embodiment of the manufacturing method of the resin pattern mentioned above, and its preferable range is also the same. In addition, the heating conditions of (2) solvent removal process are the same as that of 1st Embodiment of the manufacturing method of the resin pattern mentioned above, and its preferable range is also the same.

(3) Process of irradiating actinic light to composition by microlens array exposure machine

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 protected group contained in the component (A) is hydrolyzed.

In an exposure process, actinic light is irradiated to the board | substrate which formed the coating film through the mask which has a predetermined | prescribed pattern. After the exposure step, heat treatment (PEB) is performed as necessary, and then in the developing step, the exposure area is removed using an alkaline developer to form an image pattern.

In the present invention, the MLA exposure method is performed. An MLA exposure method is the same as that of 1st Embodiment of the manufacturing method of the resin pattern mentioned above, and its preferable range is also the same.

In order to accelerate the said hydrolysis reaction in the area | region which produced the acid catalyst, you may perform post-exposure heat processing (post baking) similarly to 1st Embodiment of the manufacturing method of the resin pattern mentioned above as needed. PEB can promote the production of carboxyl groups or phenolic hydroxyl groups from acid-decomposable groups. In the manufacturing method of the resin pattern of this invention, it is preferable to include the process of post-baking and thermosetting the said resist pattern after the said image development process and before an etching process.

In the manufacturing method of the resin pattern of this invention, it is preferable to promote hydrolysis of an acid-decomposable group without causing crosslinking reaction by performing PEB at comparatively low temperature. 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 100 degrees C or less are especially preferable. Although heating time can be set suitably according to heating temperature etc., it is preferable to set it in the range of 1 to 60 minutes.

(4) Process of developing with aqueous developer

In the developing step of (4), the polymer having a free 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 phenolic hydroxyl group which is easy to melt | dissolve in an alkaline developing solution.

In the manufacturing method of the resin pattern of this invention, it is preferable to include the post-baking process between the image development process of (4) and the etching process mentioned later, and, after the said image development process, the said resist pattern is 100-160 degreeC before an etching process. It is more preferable to include the process of post-baking in a. The effect of the etching dimensional stability improvement is obtained by heating the positive image obtained in the postbaking process after the image development process of (4).

As for the post-baking process after the said image development process but before an etching process, it is more preferable that it is 120-150 degreeC. By performing PEB at a relatively low temperature, the effect of improving the etching dimensional stability is obtained without thermally flowing the resist pattern.

Although heating time can be set suitably according to heating temperature etc., it is preferable to set it in the range of 1 to 60 minutes.

It is preferable that a basic compound is contained in the developing solution used at the image development process. As a basic compound, it is the same as that of 1st Embodiment of the manufacturing method of the resin pattern mentioned above, and its preferable range is also the same.

PH, developing time, temperature, etc. of a developing solution are the same as that of 1st Embodiment of the manufacturing method of the resin pattern mentioned above, and its preferable range is also the same.

(5) etching process

The manufacturing method of the resin pattern of this invention includes the process of etching the said board | substrate using the (5) formed resin pattern as a mask.

As a method of etching the said board | substrate using the said resin pattern as a mask, a well-known method can be used without a restriction | limiting.

<Substrate>

Although the board | substrate used for the manufacturing method of the resin pattern of this invention does not have a restriction | limiting, For example, a chromium film, a molybdenum film, a molybdenum alloy film, a tantalum film, a tantalum alloy film, an indium oxide (ITO) film doped with tin oxide, or oxidation Metal substrates such as tin films, Ni, Cu, Fe, and Al; Silicon substrates such as quartz, glass, silicon nitride film, silicon, silicon nitride, polysilicon, silicon oxide, amorphous silicon film, SOG, silicon wafer for semiconductor device production, and glass substrates for liquid crystal device production; Polymer substrates, such as a paper, a polyester film, a polycarbonate film, a polyimide film, and other polymer substrates used for an organic electroluminescence display; ceramic materials, etc. can be used. Especially, in this invention, it is preferable that it is an ITO board | substrate, a molybdenum board | substrate, or a silicon board | substrate, and it is more preferable that it is an ITO board | substrate.

The shape of a board | substrate may be plate shape, and a roll shape may be sufficient as it.

(6) Process of peeling resist pattern

The manufacturing method of the resin pattern of this invention includes the process of peeling said (6) resin pattern. As a method of peeling the said resin pattern, a well-known method can be used without a restriction | limiting in particular.

[pattern]

The pattern of this invention is a pattern obtained by etching the said board | substrate using the resist pattern obtained by hardening | curing the composition used by this invention as a mask. The pattern in this invention can be used suitably as an ITO pattern, a molybdenum pattern, or a silicon pattern, and can be used more preferably as an ITO pattern.

Since the composition used by this invention is excellent in sensitivity resolution and exposure margin, the resist pattern excellent in the formation of a square is obtained. The pattern in the present invention can be finely processed because the method for producing a resin pattern can be obtained in the present invention using the resist pattern, and the display device (especially an organic EL display device or a liquid crystal display device) has high display characteristics. You can do

[Display device]

The display device in this invention is equipped with the interlayer insulation film obtained by 1st Embodiment of the manufacturing method of the resin pattern of this invention mentioned above, or the pattern obtained by 2nd Embodiment of the manufacturing method of the resin pattern of this invention mentioned above. It features.

The display device in the present invention is not particularly limited except having a planarization film, an interlayer insulation, or a pattern formed by using the composition used in the present invention, and various known organic EL display devices and liquid crystals having various structures. And a display device.

In addition, the composition used by this invention and the cured film in 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, a spacer for keeping the thickness of the protective film of the color filter, the liquid crystal layer in the liquid crystal display device constant, or a micro lens provided on the color filter in the solid-state image sensor may be 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.

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

In addition, in order to planarize the unevenness caused by the formation of the wiring 2, the 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.

An insulating film 8 having a shape covering the periphery of the first electrode 5 is formed, and forming the insulating film 8 prevents a short between the first electrode 5 and the second electrode formed in a subsequent step. can do.

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

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

Example

Hereinafter, the present invention will be described in more detail with reference to examples. The materials, the amounts used, the ratios, the treatment contents, the treatment sequences, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific example shown below.

The following description will be made in order of the first embodiment and the second embodiment.

[First Embodiment]

In the following synthesis examples, the following codes | symbols represent the following compounds, respectively.

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

GMA: glycidyl methacrylate (wako ponyaku high school)

MAA: methacrylic acid (wako nyaku high school)

HEMA: 2-hydroxyethyl methacrylate (wako Pure Chemical Industries, Ltd.)

EDM: diethylene glycol ethyl methyl ether (Toho Kagaku Kogyo Co., Highsolve EDM)

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

<Mathf Synthesis>

Methacrylic acid (86 g, 1 mol) was cooled to 15 degreeC, and camphor sulfonic acid (4.6 g, 0.02 mol) was added. 2-dihydrofuran (71 g, 1 mol, 1.0 equivalent) was dripped at this solution. After stirring for 1 hour, saturated sodium bicarbonate (500 mL) was added, extraction was performed with ethyl acetate (500 mL), dried over magnesium sulfate, the insolubles were filtered and concentrated under reduced pressure at 40 占 폚 or lower, and the yellow oily residue was dried under reduced pressure. Distillation was carried out to obtain 125 g of tetrahydro-2H-furan-2-yl methacrylate (MATHF) having a boiling point (bp.) Of 54 to 56 ° C / 3.5 mmHg fraction as a colorless oil (yield 80%).

<Synthesis of MAEVE1>

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 was left to stand overnight at room temperature. 5 parts of sodium bicarbonate 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 filtered off, concentrated under reduced pressure at 40 占 폚 or lower, and the yellow oily substance was distilled under reduced pressure to give a boiling point (bp.). 134.0 parts of methacrylic acid 1-ethoxyethyl (MAEVE) of 43-45 degreeC / 7mmHg fraction were obtained as colorless oil.

Obtained methacrylic acid 1-ethoxyethyl (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 EDM (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 (brand name, product made from Wako Pure Chemical Industries, Ltd., 4 parts) and EDM (100.0 parts) was dripped over 2.5 hours. After completion of the dropwise addition, the mixture was reacted at 70 ° C for 4 hours to obtain an EDM solution (solid content concentration: 40%) of the polymer MAEVE1.

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

The following polymer was synthesize | combined according to the said synthesis example.

MATHF1

MAEVE2

MATHF2

MATHF3

It synthesize | combined by the method as described in Example 1 of Novolak Unexamined-Japanese-Patent No. 2003-98671.

The following were employ | adopted about the other material.

(B) acid generator

(B-1-1) CGI-1397 (brand name, a structure shown below, product made in Chiba specialty chemical company)

(B-1-2) the following compound

Synthesis of B-1-2

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

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 and then reslurried with methanol (20 mL), filtered and dried to obtain B-2 (2.3 g).

In addition, the ¹ H-NMR spectrum (300 MHz, CDCl ₃ ) of B-4 is δ = 8.3 (d, 1H), 8.0 (d, 2H), 7.9 (d, 1H), 7.8 (d, 1H), 7.6 (d, 1H), 7.4 (d, 1H), 7.3 (d, 2H), 7.1 (d. 1H), 5.6 (q, 1H), 2.4 (s, 3H), and 1.7 (d, 3H).

(B-1-3) the following onium salt (manufactured by Midori Kagaku Co., TPS-1000)

(B-1-4) the following quinonediazide

Synthesis of Naphthoquinonediazide Compounds

42.45 g of Trisp-PA (manufactured by Honshu Kagaku), 61.80 g of o-naphthoquinone diazide-5-sulfonyl chloride, and 300 ml of acetone are injected into a three-necked flask, and 24.44 g of triethylamine is added dropwise over 1 hour at room temperature. did. After the addition was completed, the mixture was stirred for 2 hours, and then the reaction solution was poured into a large amount of water while stirring. The precipitated naphthoquinone diazide sulfonic acid ester was collected by suction filtration, and vacuum dried at 40 ° C. for 24 hours to obtain the following naphthoquinone diazide compound.

Epoxy Resin: JER157S65 (Mitsubishi Kagaku Corporation)

Copolymer 1

Synthesis of Copolymer 1

After nitrogen-substituting the flask, 459.0 g of diethylene glycol dimethyl ether solutions in which 9.0 g of 2,2'-azobisisobutyronitrile was dissolved were injected. Subsequently, 22.5 g of styrene, 15.0 g of methacrylic acid, 51.5 g of dicyclopentanyl methacrylate, and 90.0 g of methacrylic acid glycidyl were injected, and then stirring was gradually started. The temperature of the solution was raised to 80 ° C. and maintained at this temperature for 5 hours, followed by heating at 90 ° C. for 1 hour to terminate the polymerization. The reaction product solution was then added dropwise to a large amount of water to solidify the reaction. The coagulum was washed with water, redissolved in 200 g of tetrahydrofuran, and coagulated again with a large amount of water. After carrying out this re-dissolution coagulation operation three times in total, the obtained coagulated product was vacuum dried at 60 ° C. for 48 hours to obtain the desired copolymer 1.

Celoxide 2021P (Diesel Kagaku Kogyo Co., Ltd.)

Coherence improver: KBM-403, Shin-Etsu Kagaku Senior High School

Sensitizer:

DBA (9,10-dibutoxy anthracene, Kawasaki Kasei Kogyo Co., Ltd.)

DETX (Kayacure-DETX Nippon Kayaku made)

Basic compound:

DBN (manufacturer: Tokyo Kasei Co., Ltd., part number: D131)

CMTU (Manufacturer: Toyo Kasei High School, Article No .: CMTU)

TPI (Made in Tokyo Kasei, T0999)

Surfactant: Perfluoroalkyl group containing nonionic surfactant represented by the following structural formula.

According to description of Table 1, each component was melt-mixed so that it might become the following composition, and it filtered with the polytetrafluoroethylene filter of 0.2 micrometer of diameters, and obtained the composition for insulating material.

<Composition>

(A) Polyethylene glycol methyl ether acetate of resin [hereinafter abbreviated as PGMEA. Solvent (C) component] Solution (A) 100.0 parts by resin solids

(B) 2.0 parts of photoacid generator

2.0 parts epoxy resin

0.5 parts of adhesion modifier

Basic compound

0.1 part of basic compound (1)

0.02 parts of basic compound (2)

0.02 part surfactant

15.0 parts when adding a photosensitizer (quinonediazide compound)

<Sensitivity>

The composition was apply | coated to the glass substrate which wash | cleaned and the hexamethyldisilazane (HMDS) process so that it might become a film thickness of 3.0 micrometers.

Subsequently, an MLA (Micro Lens Array) type exposure machine (manufactured by V Technology Co., Ltd., microlens made of four quartz members, 130 µm diameter and 150 µm pitch) using an ultra-high pressure mercury lamp was used, and the projection magnification was 1 :. 1, The MLA chip was placed between the sample substrate and the photomask and subjected to scan exposure. The photomask was exposed at an exposure wavelength (ghi line) in a state in which the quartz exposure mask having a circular hole pattern of 10 µm and the color filter substrate arranged so that the mask and the photosensitive resin layer faced each other were substantially parallel. In the MPA exposure system in the comparative example, it exposed on the same conditions using the mirror projection aligner type exposure machine (MPA-5500CF by Canon Corporation) which has an ultrahigh pressure mercury lamp. Subsequently, shower development was carried out at a cone nozzle pressure of 0.18 MPa for 60 seconds at 23 ° C. using a TMAH developer (0.5% tetramethylammonium hydride) to form a pattern. Subsequently, using a rinsing treatment (pure water), it sprayed in the shower at the cone type nozzle pressure of 0.18 Mpa for 20 second at 23 degreeC, and the residue around the formed pattern was removed, and the line and space pattern was formed (patterning process).

Subsequently, after exposing (post-exposure) the board | substrate with a hole pattern at 300mJ / cm <2>, heat processing was performed for 30 minutes at 230 degreeC (heat processing process), and the interlayer insulation film was produced on the glass substrate.

Sensitivity was evaluated as the exposure amount for which the hole diameter of a resist becomes 10 micrometers exactly as an optimal exposure amount.

1 point: 200 mJ / ㎠ or more exposure dose is required

2 points | pieces: The exposure amount of 100 mJ / cm <2> or more and less than 200 mJ / cm <2> is required

3 points | pieces: The exposure amount of 50 mJ / cm <2> or more and less than 100 mJ / cm <2> is required

4 points | pieces: The exposure amount of 30 mJ / cm <2> or more and less than 50 mJ / cm <2> is required

5 points: Possible exposure dose less than 30mJ / ㎠

<Resolution>

The composition was apply | coated to the glass substrate which wash | cleaned and the hexamethyldisilazane (HMDS) process so that it might become a film thickness of 3.0 micrometers.

Subsequently, an MLA (Micro Lens Array) type exposure machine (manufactured by V Technology Co., Ltd., microlens made of four quartz members, 130 µm diameter and 150 µm pitch) using an ultra-high pressure mercury lamp was used, and the projection magnification was 1 :. 1, The MLA chip was placed between the sample substrate and the photomask to be subjected to scan exposure. Exposure wavelength (ghi line) with the quartz exposure mask which has a circular hole pattern in 0.5 micrometer interval from 1 micrometer to 10 micrometers in a photomask, and the color filter substrate arrange | positioned so that the said mask and the photosensitive resin layer may face in parallel. It exposed at 34mJ / cm <2> of exposure doses. In the MPA exposure system in the comparative example, it exposed on the same conditions using the mirror projection aligner type exposure machine (MPA-5500CF by Canon Corporation) which has an ultrahigh pressure mercury lamp.

Subsequently, shower development was carried out at a cone nozzle pressure of 0.18 MPa for 60 seconds at 23 ° C. using a TMAH developer (0.5% tetramethylammonium hydride) to form a pattern. Subsequently, using a rinse treatment (pure water), the spray was sprayed with a cone nozzle pressure of 0.18 MPa for 20 seconds at 23 ° C., and residues around the formed pattern were removed to form a line and space pattern (patterning step).

Subsequently, after exposing (post-exposure) the board | substrate with a hole pattern at 300mJ / cm <2>, heat processing was performed for 30 minutes at 230 degreeC (heat processing process), and the interlayer insulation film was produced on the glass substrate.

The hole diameter of the smallest resolvable pattern among the hole patterns was taken as the resolution.

1 point: 4.5 micrometers does not resolve

2 points | pieces: 4.5 micrometers resolve but 3.5 micrometers do not

3 points | pieces: 3.5 micrometers resolve but 3.0 micrometers do not

4 points: 3.0 micrometers resolves but 2.5 micrometers does not

5 points | pieces: 2.5 micrometers or less are resolved.

<Residue>

The composition was apply | coated to the glass substrate which wash | cleaned and the hexamethyldisilazane (HMDS) process so that it might become a film thickness of 3.0 micrometers.

Subsequently, an MLA (Micro Lens Array) type exposure machine (manufactured by V Technology Co., Ltd., microlens made of four quartz members, 130 µm diameter and 150 µm pitch) using an ultra-high pressure mercury lamp was used, and the projection magnification was 1 :. 1, The MLA chip was placed between the sample substrate and the photomask to be subjected to scan exposure. Exposure at 34mJ / cm2 at an exposure wavelength (ghi line) with a quartz exposure mask having a circular hole pattern of 10 占 퐉 in a photomask and a color filter substrate arranged so that the mask and the photosensitive resin layer face each other. did. In the MPA exposure system in the comparative example, it exposed on the same conditions using the mirror projection aligner type exposure machine (MPA-5500CF by Canon Corporation) which has an ultrahigh pressure mercury lamp.

Subsequently, shower development was carried out at a cone nozzle pressure of 0.18 MPa for 60 seconds at 23 ° C. using a TMAH developer (0.5% tetramethylammonium hydride) to form a pattern. Subsequently, using rinsing treatment (pure water), it sprayed in shower at the cone nozzle pressure of 0.18 Mpa for 20 second at 23 degreeC, the residue of the periphery of the formed pattern was removed, and the line end space pattern was formed (patterning process).

Subsequently, after exposing (post-exposure) the board | substrate with a hole pattern at 300mJ / cm <2>, heat processing was performed for 30 minutes at 230 degreeC (heat processing process), and the interlayer insulation film was produced on the glass substrate. The hole part of 10 micrometer diameter was observed with the scanning electron microscope (SEM) at the magnification of 10,000 times, and the presence or absence of the residue was investigated.

1 point: A large amount of residue

2 points | pieces: There is a residue near the center of a hall

3 points | pieces: A residue exists in the boundary part with the interlayer insulation film around a hole.

4 points | pieces: There exists a little residue at the boundary part with the interlayer insulation film around a hole.

5 points | pieces: A residue is not observed

<General performance>

Based on the said sensitivity resolution and the result of a residue, it evaluated comprehensively as follows.

The total performance sensitivity resolution and the evaluation score of the residue were totaled, and the overall performance was evaluated according to the following criteria.

1 point: 1-5 points in total

2 points: 6-9 points in total

3 points: 10-11 points in total

4 points: Total 12 to 13 points

5 points: 14 points or more

(Example 1-14)

Except having changed the board | substrate into the silicon wafer from the glass substrate using the composition of Example 1-1, it carried out about the composition of Example 1-1. As a result, the same result as in Example 1-1 was obtained.

(Example 1-15)

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, while covering the TFT (1) thereby forming the insulating film 3 made of Si ₃ N _4. Subsequently, a contact hole (not shown here) was formed in the insulating film 3, and then a wiring 2 (1.0 μm in height) connected to the TFT 1 through the contact hole was formed on the insulating film 3. . This wiring 2 is for connecting the TFT 1 with the organic EL element formed between the TFTs 1 or in a later step.

In addition, in order to planarize the unevenness caused by the formation of the wiring 2, the planarization layer 4 was formed on the insulating film 3 in a state of filling the unevenness of the wiring 2. Formation of the planarization film 4 onto the insulating film 3 was performed by spin-coating the composition of Example 1 on a substrate, prebaking (90 ° C. × 2 minutes) on a hot plate, using an MLA exposure machine from the mask image. After irradiating i line | wire (365 nm) to 45 mJ / cm <2> (roughness 20mW / cm <2>), it developed in alkaline aqueous solution, the pattern was formed, and the heat processing for 60 minutes was performed at 230 degreeC. The applicability | paintability at the time of apply | coating the said composition was favorable, and generation | occurrence | production of a wrinkle and a crack was not recognized in the cured film obtained after exposure, image development, and film-forming. Moreover, the film thickness of the planarization film 4 which produced 500 nm of average level | step differences of the wiring 2 was 2,000 nm.

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

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

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

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

(Example 1-16)

In the active matrix liquid crystal display device of FIGS. 1 and 2 of Japanese Patent No. 3321003, a cured film 17 was formed as an interlayer insulating film as follows to obtain a liquid crystal display device of Example 1-16.

That is, using the composition of Example 1-1, the cured film 17 is formed as an interlayer insulating film by a method similar to the method of forming the planarization film 4 of the organic EL display device in Example 1-15. did.

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

[Second Embodiment]

(Synthesis Example-1)

32.4 g (0.2 mol) of p-acetoxystyrene was dissolved in 120 ml of butyl acetate, and 0.033 g of azobisisobutyronitrile (AIBN) was added three times at an interval of 2.5 hours at 80 ° C under nitrogen stream and stirring. The polymerization reaction was performed by continuing stirring for 5 hours. The reaction solution was poured into 1200 ml of hexane to precipitate a white resin. The obtained resin was dried and dissolved in 150 ml of methanol. An aqueous solution of 7.7 g (0.19 mol) of sodium hydroxide / 50 ml of water was added thereto and hydrolyzed by heating under reflux for 3 hours. Thereafter, 200 ml of water was added thereto to dilute, neutralized with hydrochloric acid to precipitate a white resin. This resin was separated by filtration and washed with water and dried. Furthermore, it melt | dissolved in 200 ml of tetrahydrofuran, was dripped, and reprecipitation was carried out stirring vigorously in 5 liter of ultrapure water. This reprecipitation operation was repeated three times. The obtained resin was dried in a vacuum dryer at 120 ° C. for 12 hours to obtain a poly (p-hydroxystyrene) alkali-soluble resin (R-1). The weight average molecular weight of obtained resin was 12,000.

Synthesis Example-2 Synthesis of Polymer (A-1)

20 g of alkali-soluble resin (R-1) and 320 g of propylene glycol monomethyl ether acetate (PGMEA) obtained in Synthesis Example-1 were dissolved in a flask, distilled under reduced pressure, and azeotropic distillation of water and PGMEA. After confirming that the water content was sufficiently lowered, 24 g of ethyl vinyl ether and 0.35 g of p-toluenesulfonic acid were added, followed by stirring at room temperature for 1 hour. 0.28g of triethylamine was added there and reaction was stopped. Ethyl acetate was added to the reaction solution, followed by further washing with water, followed by distillation under reduced pressure to distill off PGMEA of ethyl acetate, water and azeotrope to obtain polymer (A-1), which was an alkali-soluble resin protected with an acid-decomposable group.

The structure of the polymer (A-1) is 1-ethoxyethyl group protector / p-hydroxystyrene copolymer (PHS-EVE) of p-hydroxy styrene.

The following compound was synthesize | combined according to the method similar to the above.

Polymer (A-2)

Polymer (A-3)

Polymer (A-4)

Polymer (A-5) It synthesize | combined by the method similar to Example 1 of Unexamined-Japanese-Patent No. 2003-98671.

Polymer (A-6)

Polymer A-6 which is a copolymer (A) was synthesize | combined 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 was left to stand overnight at room temperature. 5 parts of sodium bicarbonate 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 filtered off, and concentrated under reduced pressure at 40 占 폚 or lower. The yellow oily residue was distilled under reduced pressure to obtain a boiling point (bp. 134.0 parts of methacrylic acid 1-ethoxyethyl (MAEVE) of 43-45 degreeC / 7mmHg fraction were obtained as a colorless oily substance.

Obtained methacrylic acid 1-ethoxyethyl (63.28 parts (0.4 molar equivalent)), BzMA (52.83 parts (0.3 molar equivalent)), MAA (8.61 parts (0.1 molar equivalent)), HEMA (26.03 parts (0.2 molar equivalent) ) And EDM (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 (brand name, product made from Wako Pure Chemical Industries, Ltd., 4 parts) and EDM (100.0 parts) was dripped over 2.5 hours. After dripping was completed, EDM solution (solid content concentration: 40%) of polymer A-1 was obtained by making it react at 70 degreeC for 4 hours.

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

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

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

Bzma: benzyl methacrylate (wako nyaku high school)

MAA: methacrylic acid (wako nyaku high school)

HEMA: 2-hydroxyethyl methacrylate (wako Pure Chemical Industries, Ltd.)

EDM: diethylene glycol ethyl methyl ether (Toho Kagaku Kogyo Co., Highsolve EDM)

Polymer (A-7) It synthesize | combined similarly to said (A-6).

The other raw material used the following.

Acid generator (B-1-1): CGI-1397 (brand name, product made in Chiba specialty chemical company)

Acid generator (B-1-3): Onium salt (manufactured by Midori Kagaku Co., TPS-1000)

Acid generator (B-2-1): It synthesize | combined according to the method of Paragraph No. 0108 of Unexamined-Japanese-Patent No. 2002-528451.

Ts part represents a tosyl group.

Acid generator (B-2-2): naphthoquinone diazide (NQD) (made by Daito Chemical Co., Ltd., DTEP-250)

Basic Compound (CMTU): (Toyo Kasei Co., Ltd., CMTU)

Basic compound (DBN): (made by Tokyo Kasei Co., Ltd., D131)

Basic compound (TPI): (made by Tokyo Kasei Co., Ltd., T0999)

Sensitizer: DBA (Kawasaki Kasei Co., Ltd., 9,10-dibutoxy anthracene)

According to description of Table 1, each component was melt-mixed so that it might become the following composition, and it filtered with the polytetrafluoroethylene filter of 0.2 micrometer of diameters, and obtained the composition of the Example and the comparative example.

<Composition>

Copolymer (A): Polyethylene glycol methyl ether acetate solution of polymer A-1

100.0 parts by solids

Mine generator (B) 2.0 parts

0.2 parts of basic compound (C)

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

When adding a sensitizer, 1.0 part was mix | blended.

Each evaluation shown below was performed about the composition of the obtained Example and a comparative example.

<Sensitivity>

The composition was apply | coated to the glass substrate which wash | cleaned and the hexamethyldisilazane (HMDS) process so that it might become a film thickness of 1.3 micrometers.

Subsequently, an MLA (Micro Lens Array) type exposure machine (manufactured by V Technology Co., Ltd., microlens made of four quartz members, 130 µm diameter and 150 µm pitch) using an ultra-high pressure mercury lamp was used, and the projection magnification was 1 :. 1, The MLA chip was placed between the sample substrate and the photomask to be subjected to scan exposure. The photomask was exposed at an exposure wavelength (ghi line) in a state in which the quartz exposure mask having a linear image pattern of a line and space of 10 µm and the color filter substrate arranged so that the mask and the photosensitive resin layer faced each other were substantially parallel. . In the MPA exposure system in the comparative example, it exposed on the same conditions using the mirror projection aligner type exposure machine (MPA-5500CF by Canon Corporation) which has an ultrahigh pressure mercury lamp.

Subsequently, puddle development was carried out at 23 ° C. for 60 seconds using a TMAH developer (2.38% tetramethylammonium hydride) to form a pattern. Subsequently, using rinsing treatment (pure water), it sprayed in shower at the cone nozzle pressure of 0.06 Mpa for 20 second at 23 degreeC, the residue of the periphery of the formed pattern was removed, and the line end space pattern was formed (patterning process).

The sensitivity was evaluated using the exposure amount whose space line width of the resist formed with the 10 micrometers line and space pattern exactly 10 micrometers as an optimal exposure amount.

1 point: A dose of 100 mJ / cm 2 or more is required

2 points | pieces: The exposure amount of 50 mJ / cm <2> or more and less than 100 mJ / cm <2> is required

3 points | pieces: The exposure amount of more than 20mJ / cm <2> and less than 50mJ / cm <2> is required

4 points | pieces: The exposure dose of 10 mJ / cm <2> or more and less than 20 mJ / cm <2> is required

5 points: possible at an exposure dose of less than 10 mJ / ㎠

<Resolution>

The composition was apply | coated to the glass substrate which wash | cleaned and the hexamethyldisilazane (HMDS) process so that it might become a film thickness of 1.3 micrometers.

Subsequently, a MLA (Micro Lens Array) type exposure machine (manufactured by V Technology Co., Ltd., a microlens made of four quartz members, 130 µm diameter and 150 µm pitch) using an ultra-high pressure mercury lamp was used, and the projection magnification was 1 :. 1, The MLA chip was placed between the sample substrate and the photomask to be subjected to scan exposure. Exposure wavelength in a state in which the photomask is substantially parallel to a quartz exposure mask having a linear image pattern of line and space at a interval of 0.5 µm from 1 µm to 10 µm, and a color filter substrate arranged such that the mask and the photosensitive resin layer face each other. It exposed at the exposure amount 34mJ / cm <2> by (ghi line). It exposed on the same conditions using the mirror projection aligner type exposure machine (MPA-5500CF by Canon Corporation) which has an ultrahigh pressure mercury lamp.

Subsequently, using a TMAH developer (2.38% tetramethylammonium hydride), puddle development at 23 ° C. for 60 seconds to form a pattern image. Subsequently, using rinsing treatment (pure water), it sprayed in shower at the cone nozzle pressure of 0.06 Mpa for 20 second at 23 degreeC, the residue of the periphery of the formed pattern was removed, and the line end space pattern was formed (patterning process).

The line width of the smallest resolvable pattern among the line and space patterns was taken as the resolution.

1 point: 3.0 micrometers is not resolved.

2 points | pieces: 3.0 micrometers is resolved, but 2.5 micrometers or less are not resolved.

3 points | pieces: 2.5 micrometers resolved but 2.0 micrometers or less do not resolve.

4 points | pieces: 2.0 micrometers is resolved, but 1.5 micrometers or less are not resolved.

5 points | pieces: 1.5 micrometers is resolved.

<Residue>

The composition was apply | coated to the glass substrate which wash | cleaned and the hexamethyldisilazane (HMDS) process so that it might become a film thickness of 1.3 micrometers.

Subsequently, an MLA (Micro Lens Array) type exposure machine (manufactured by V Technology Co., Ltd., microlens made of four quartz members, 130 µm diameter and 150 µm pitch) using an ultra-high pressure mercury lamp was used, and the projection magnification was 1 :. 1, The MLA chip was placed between the sample substrate and the photomask to be subjected to scan exposure. Exposure amount 34mJ at an exposure wavelength (ghi line) in a state where the quartz exposure mask having a line-and-space linear image pattern of 5 µm in a photomask and the color filter substrate arranged so that the mask and the photosensitive resin layer face each other are substantially parallel. It exposed at / cm <2>. It exposed on the same conditions using the mirror projection aligner type exposure machine (MPA-5500CF by Canon Corporation) which has an ultrahigh pressure mercury lamp.

Subsequently, using a TMAH developer (2.38% tetramethylammonium hydride), puddle development at 23 ° C. for 60 seconds to form a pattern image. Subsequently, using rinsing treatment (pure water), it sprayed in shower at the cone nozzle pressure of 0.06 Mpa for 20 second at 23 degreeC, the residue of the periphery of the formed pattern was removed, and the line end space pattern was formed (patterning process).

It observed by the scanning electron microscope (SEM) at the magnification of 10,000 times, and investigated the presence or absence of the residue.

1 point | piece: The residue generate | occur | produces in large quantities.

2 points | pieces: There is a residue near the center of space.

3 points | pieces: The residue exists at the boundary of a line and a space.

4 points | pieces: There is a little residue at the boundary of a line and a space.

5 points | pieces: A residue is not observed.

<General performance>

Based on the said sensitivity resolution and the result of a residue, it evaluated comprehensively as follows.

Overall performance, sensitivity resolution, and the evaluation score of the residue were summed up, and overall performance was evaluated according to the following criteria.

1 point: 1-5 points in total

2 points: 6-9 points in total

3 points: 10-11 points in total

4 points: Total 12 to 13 points

5 points: 14 points or more

As apparent from the above table, it was found that the composition used in the present invention was excellent in sensitivity resolution and residue overall when exposed to an MLA exposure machine (Examples 2-1 to 2-10). In particular, when the basic compound represented by General formula (a) was employ | adopted as a basic compound, it turned out that an effect is remarkable.

On the other hand, even when using the composition in this invention, when it exposed by MPA exposure machine, it turned out that these performances are inferior (Comparative Example 2-2, 2-3).

Moreover, even if it exposed by MLA exposure machine, when the acid generator was not oxime sulfonate, it turned out that these performances are inferior (comparative example 2-4).

[Example 2-11]

(Organic EL display device)

An organic EL display device having an ITO pattern was produced by the following method (see FIG. 1).

Forming a glass substrate 6, a bottom gate type TFT (1) on, and in a state covering the TFT (1) thereby forming the insulating film 3 made of Si ₃ N _4. Subsequently, a contact hole (not shown here) was formed in the insulating film 3, and then a wiring 2 (1.0 μm in height) connected to the TFT 1 through the contact hole was formed on the insulating film 3. . This wiring 2 is for connecting the TFT 1 with the organic EL element formed between the TFTs 1 or in a later step.

In addition, in order to planarize the unevenness caused by the formation of the wiring 2, the planarization film 4 was formed on the insulating film 3 in a state where the unevenness by the wiring 2 was filled up. Formation of the planarization film 4 onto the insulating film 3 was carried out by spin-coating the composition described in Example 1 of JP-A-2009-98616 on a substrate and prebaking (90 ° C. × 2 minutes) on a hot plate. After that, using an MLA exposure machine, i-line (365 nm) was irradiated with 45 mJ / cm 2 (roughness 20 mW / cm 2) on a mask using a high pressure mercury lamp, and then developed with an aqueous alkali solution to form a pattern, followed by heating at 230 ° C. for 60 minutes. Processing was performed.

The applicability | paintability at the time of apply | coating a composition was favorable, and neither the wrinkle nor the crack generate | occur | produced in the cured film obtained after exposure, image development, and film-forming. Moreover, the film thickness of the planarization film 4 which produced 500 nm of average level | step differences of the wiring 2 was 2,000 nm.

Subsequently, a bottom emission type organic EL device was formed on the obtained planarization film 4. First, on the planarization film 4, the 1st electrode 5 which consists of ITO was connected to the wiring 2 through the contact hole 7, and was formed. The composition of Example 1 was then spin-coated onto an ITO substrate, prebaked on a hot plate (90 ° C. × 2 minutes), and then the i-ray (365 nm) was exposed to 20 mJ / m using a high pressure mercury lamp on a mask with an MLA exposure machine. After irradiating 2 cm <2> (roughness 20mW / cm <2>), it developed by aqueous alkali solution and formed the pattern. Thereafter, a postbaking heat treatment was performed at 140 ° C. for 3 minutes before the etching step. ITO pattern processing was performed by the wet etchant by immersing 40 degreeC / 1min in ITO etchant (3% oxalic acid aqueous solution) using this resist pattern as a mask. Then, the said resist pattern was stripped off by immersing at 70 degreeC / 7min in the resist stripping liquid (MS2001, the product made by Fujifilm Electronics). 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 8 by the method similar to the above using the composition of Example 1 of Unexamined-Japanese-Patent No. 2009-98616. By forming this insulating film 8, the short between the 1st electrode 5 and the 2nd electrode formed in a later process can be prevented.

Further, a hole transport layer, an organic light emitting layer, and an electron transport layer were sequentially formed in a vacuum deposition apparatus via a desired pattern mask. Next, 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 sticking using the sealing glass plate and an ultraviolet curable epoxy resin.

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

Example 2-12

(Liquid crystal display device)

The liquid crystal display device provided with an ITO pattern was produced with the following method.

In the active-matrix liquid crystal display device of FIG. 1 of Unexamined-Japanese-Patent No. 3321003, the cured film 17 was formed as an interlayer insulation film as follows, and the liquid crystal display device of Example 21 was obtained.

That is, 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 20.

As a result of applying a drive voltage to the obtained liquid crystal display device with an ITO pattern, 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 (20)

(1) Process of apply | coating the composition containing resin which (A) acid solubility increases by action of acid, (B) oxime sulfonate system photoacid generator, and (C) solvent on board | substrate,
(2) removing the solvent from the applied composition;
(3) exposing the composition to irradiated actinic light with a microlens array exposure machine, and
(4) The manufacturing method of the resin pattern characterized by including the process of image development with an aqueous developing solution. The method of claim 1,
The resin in which alkali solubility is increased by the action of the (A) acid is a structural unit derived from a monomer having a protective carboxyl group protected with an acid decomposable group and / or a structural unit derived from a monomer having a protected phenolic hydroxyl group protected with an acid decomposable group ( A method for producing a resin pattern, comprising a polymer containing a1). 3. The method according to claim 1 or 2,
The structural unit derived from the monomer having a protective carboxyl group protected with the acid-decomposable group and / or the protective phenolic hydroxyl group protected with the acid-decomposable group is a structural unit derived from the monomer having a protective carboxyl group protected with acetal and / or a protective phenol protected with acetal. It is a structural unit derived from the monomer which has a hydroxyl group, The manufacturing method of the resin pattern characterized by the above-mentioned. 3. The method according to claim 1 or 2,
Resin whose alkali solubility increases by the action of said (A) acid has a structural unit represented with the following general formula (a1-1), and / or a structural unit represented with the following general formula (V), It is characterized by the above-mentioned. Method of making a pattern.

[In Formula (a1-1), R ¹²¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, L ¹ represents a carbonyl group or a phenylene group, and R ¹²² to R ¹²⁸ each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, respectively. Indicates

[Ra ¹ to Ra ⁶ in General Formula (V) are each a hydrogen atom, an alkyl group which may have a substituent having 1 to 20 carbon atoms, or an aryl group which may have a substituent, and may be bonded to each other to form a ring. Ra ⁷ is a hydrogen atom or a methyl group, and Ra ⁸ is a halogen atom, a hydroxyl group or an alkyl group having 1 to 3 carbon atoms. n1 is an integer of 0 to 4] The method of claim 3, wherein
Resin whose alkali solubility increases by the action of said (A) acid has a structural unit represented with the following general formula (a1-1), and / or a structural unit represented with the following general formula (V), It is characterized by the above-mentioned. Method of making a pattern.

[In Formula (a1-1), R ¹²¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, L ¹ represents a carbonyl group or a phenylene group, and R ¹²² to R ¹²⁸ each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, respectively. Indicates

[Ra ¹ to Ra ⁶ in General Formula (V) are each a hydrogen atom, an alkyl group which may have a substituent having 1 to 20 carbon atoms, or an aryl group which may have a substituent, and may be bonded to each other to form a ring. Ra ⁷ is a hydrogen atom or a methyl group, and Ra ⁸ is a halogen atom, a hydroxyl group or an alkyl group having 1 to 3 carbon atoms. n1 is an integer of 0 to 4] 3. The method of claim 2,
The resin in which alkali solubility increases by the action of said (A) acid contains the structural unit (a2) derived from the monomer which has a crosslinking group, The manufacturing method of the resin pattern characterized by the above-mentioned. The method of claim 3, wherein
The resin in which alkali solubility increases by the action of said (A) acid contains the structural unit (a2) derived from the monomer which has a crosslinking group, The manufacturing method of the resin pattern characterized by the above-mentioned. 3. The method according to claim 1 or 2,
Resin whose alkali solubility increases by the action of said (A) acid contains the polymer containing the structural unit represented by the following general formula (a1-1), and the structural unit (a2) derived from the monomer which has a crosslinking group. The manufacturing method of the resin pattern characterized by the above-mentioned.

[In Formula (a1-1), R ¹²¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, L ¹ represents a carbonyl group or a phenylene group, and R ¹²² to R ¹²⁸ each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, respectively. Indicates 3. The method according to claim 1 or 2,
(D) The manufacturing method of the resin pattern characterized by further containing a basic compound. The method of claim 9,
The said (D) basic compound is a compound represented by the following general formula (a), The manufacturing method of the resin pattern characterized by the above-mentioned.
Formula (a)

[In General Formula (a), R <^2> represents the linear or branched alkyl group which may have a C1-C6 substituent, or the cyclic alkyl group which may have a C3-C10 substituent. X represents an oxygen atom or a sulfur atom. Y ¹ represents an oxygen atom or an -NH- group. p1 represents an integer of 1 to 3] 3. The method according to claim 1 or 2,
Said (B) oxime sulfonate-type photo-acid generator is an oxime sulfonate-type acid generator represented with the following general formula (B2) or (B3), The manufacturing method of the resin pattern characterized by the above-mentioned.
General formula (B2)

[In formula (B2), R <^42> represents an alkyl group or an aryl group, X represents an alkyl group, an alkoxy group, or a halogen atom, m4 represents the integer of 0-3, and when m4 is 2 or 3, several X is the same. May be different]
General formula (B3)

[In formula (B3), R <^43> represents an alkyl group or an aryl group, X <^1> represents a halogen atom, a hydroxyl group, a C1-C4 alkyl group, a C1-C4 alkoxy group, a cyano group, or a nitro group, n4 is 0-5. Represents an integer of 3. The method according to claim 1 or 2,
The composition is a method for producing a resin pattern, characterized in that the composition for an interlayer insulating film. 3. The method according to claim 1 or 2,
The composition is a method for producing a resin pattern, characterized in that the composition for etching resist. 3. The method according to claim 1 or 2,
The composition further comprises at least one of a sensitizer, an epoxy resin, an adhesion improving agent, a basic compound and a surfactant. 3. The method according to claim 1 or 2,
The method of manufacturing a resin pattern further comprising the step of post-baking after the step of developing with the aqueous developer (4). After the process of developing by the said (4) aqueous developing solution containing the manufacturing method of the resin pattern of any one of Claims 1-14.
(5) a step of etching the substrate using the formed resin pattern as a mask, and
(6) The manufacturing method of the pattern board characterized by including the process of peeling the said resin pattern. 17. The method of claim 16,
Resin which alkali solubility increases by the action of said (A) acid has a structural unit represented by the said General formula (V) as a repeating unit, The manufacturing method of the pattern board | substrate characterized by the above-mentioned. The manufacturing method of the interlayer insulation film containing the manufacturing method of the resin pattern of any one of Claims 1-15. The manufacturing method of the resin pattern of any one of Claims 1-15, the manufacturing method of the pattern substrate of Claim 16 or 17, or the manufacturing method of the interlayer insulation film of Claim 18 characterized by the above-mentioned. The manufacturing method of a thin film transistor board | substrate. The manufacturing method of the resin pattern of any one of Claims 1-15, the manufacturing method of the pattern substrate of Claim 16 or 17, or the manufacturing method of the interlayer insulation film of Claim 18 characterized by the above-mentioned. The manufacturing method of the display apparatus made into.

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