JP5112772B2 - Positive photoresist composition for manufacturing liquid crystal element and method for forming resist pattern - Google Patents

Description

  The present invention relates to a positive photoresist composition for producing a liquid crystal element and a resist pattern forming method.

  A resist pattern is usually used for patterning in the field of liquid crystal device (LCD) manufacturing. The resist pattern is generally formed by applying a photoresist composition on a support such as a substrate to form a resist film, subjecting the resist film to selective exposure, and then developing with alkali.

  2. Description of the Related Art Conventionally, in the field of LCD manufacturing, as a method for applying a positive photoresist composition, a coating method that spins after dropping in the center is frequently used (see, for example, Non-Patent Document 1).

In particular, in the field of LCD manufacturing, substrates tend to increase in size year by year. For example, in the case of a large substrate of 1 m square class, the amount of positive photoresist composition that is shaken off during rotation (during spinning) and discarded is considerably increased. It has become difficult to meet demands other than the uniformity of the resist film thickness, such as the problem of ensuring tact time.
From such a current situation, as a new positive photoresist composition coating method applicable to a fourth generation substrate (680 mm × 880 mm) or later, particularly a large substrate after the fifth generation substrate (1000 mm × 1200 mm to 1280 mm × 1400 mm or so). A resist coating method using a discharge nozzle method has been proposed.

The discharge nozzle type resist coating method is a method in which a positive photoresist composition is applied to the entire coated surface of a support by moving the discharge nozzle and the support relatively.
As a resist coating method by a discharge nozzle method, for example, a method using a discharge nozzle that has a discharge port in which a plurality of nozzle holes are arranged in a row or a slit-like discharge port and can discharge a positive photoresist composition in a strip shape. Has been proposed. In addition, a method of adjusting the film thickness by applying a positive photoresist composition to the entire coated surface of the support by the discharge nozzle method and then spinning the support is proposed.

Further, as a means for improving the coating property when coated on a support such as a substrate, a positive photoresist in which a surfactant, for example, perfluorooctanoic acid (PFOA), perfluorooctanesulfonic acid (PFOS) or the like is blended. Although the composition is known, in recent years, the demand for non-PFOA and non-PFOS is increasing, and switching to non-PFOA and non-PFOS surfactants is desired.
Electric Journal August 2002, pages 121-123

In recent years, the size of a substrate serving as a support has been increased. While the support is required to improve the resist pattern shape and various lithography characteristics, in order to perform desired patterning with high accuracy, the thickness of the resist film is made uniform over the entire surface of the support. This is one of the important issues.
However, the conventional positive photoresist composition has a problem that the resist film swells (hereinafter referred to as “edge bead”) at the edge portion of the support, for example, and the film thickness of the resist film tends to be non-uniform. .

  The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a positive photoresist composition for manufacturing a liquid crystal element and a resist pattern forming method capable of improving the uniformity of the film thickness of a resist film. And

［式（Ｅ１−０）中、Ｒ ^ｆ は炭素原子数１〜６のフッ素化アルキル基であり、Ｒ ^１１ は炭素原子数１〜５のアルキレン基である。］ As a result of intensive studies, the present inventors have found that the above problems can be solved by using a positive photoresist composition containing a specific surfactant, and have completed the present invention.
That is, the first aspect of the present invention includes an alkali-soluble novolak resin (A), a naphthoquinonediazide group-containing compound (C), an organic solvent (D), and a group represented by the following general formula (E1-0). A positive photoresist composition for producing a liquid crystal device, comprising a fluorine-based surfactant (E1) having an alkylene oxide chain.

[In Formula (E1-0), R ^f is a fluorinated alkyl group having 1 to 6 carbon atoms, and R ¹¹ is an alkylene group having 1 to 5 carbon atoms. ]

［式（Ｅ１−０）中、Ｒ^ｆは炭素原子数１〜６のフッ素化アルキル基であり、Ｒ^１１は炭素原子数１〜５のアルキレン基または単結合である。］ The second aspect of the present invention is an alkali-soluble novolak resin (A), a naphthoquinonediazide group-containing compound (C), an organic solvent (D), and an alkylene containing a group represented by the following general formula (E1-0). A positive photoresist composition for producing a liquid crystal device, comprising a fluorine-based surfactant (E1) having an oxide chain and a silicon-based surfactant (E2).

[In Formula (E1-0), R ^f represents a fluorinated alkyl group having 1 to 6 carbon atoms, and R ¹¹ represents an alkylene group having 1 to 5 carbon atoms or a single bond. ]

According to a third aspect of the present invention, there is provided a positive photoresist composition for manufacturing a liquid crystal device according to the first or second aspect over the entire coated surface of the support by relatively moving the discharge nozzle and the support. A resist pattern forming method including a step of applying a resist, a step of forming a resist film on the support, a step of exposing the resist film, and a step of forming the resist film by alkali development.

In the present specification and claims, the “structural unit” means a monomer unit (monomer unit) constituting a resin component (polymer, copolymer).
Unless otherwise specified, the “alkyl group” includes linear, branched, and cyclic monovalent saturated hydrocarbon groups.
The “alkylene group” includes straight-chain, branched-chain, and cyclic divalent saturated hydrocarbon groups unless otherwise specified.
“Lower alkyl group” means an alkyl group having 1 to 5 carbon atoms.
“Exposure” includes not only light irradiation but also general irradiation of radiation such as an electron beam.
The “support surface of the support” refers to a region of the support to which the positive photoresist composition is to be applied, and generally means the entire surface of the support.

  INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a positive photoresist composition for manufacturing a liquid crystal element and a resist pattern forming method that can improve the uniformity of the resist film thickness.

≪Positive photoresist composition for liquid crystal element manufacturing≫
The positive photoresist composition for producing a liquid crystal device of the present invention comprises an alkali-soluble novolak resin (A) (hereinafter referred to as “component (A)”), a naphthoquinonediazide group-containing compound (C) (hereinafter referred to as “component (C)”). , An organic solvent (D) (hereinafter referred to as component (D)), and a fluorine-based surfactant (E1) having an alkylene oxide chain containing a group represented by the general formula (E1-0) (hereinafter referred to as ( E1) component)).

<(A) component>
In the present invention, the component (A) is an alkali-soluble novolak resin, which can be arbitrarily selected from those that can be normally used as a film-forming substance in a positive photoresist composition.
Specific examples of the component (A) include novolak resins obtained by reacting phenols and aldehydes in the presence of an acidic catalyst.

Examples of the phenols include phenol; cresols such as m-cresol, p-cresol, and o-cresol; 2,3-xylenol, 2,5-xylenol, 3,5-xylenol, 3,4-xylenol, and the like. Xylenols; m-ethylphenol, p-ethylphenol, o-ethylphenol, 2,3,5-trimethylphenol, 2,3,5-triethylphenol, 4-tert-butylphenol, 3-tert-butylphenol, 2- alkylphenols such as tert-butylphenol, 2-tert-butyl-4-methylphenol, 2-tert-butyl-5-methylphenol; p-methoxyphenol, m-methoxyphenol, p-ethoxyphenol, m-ethoxyphenol, p-propoxy Alkoxyphenols such as phenol and m-propoxyphenol; isopropenylphenols such as o-isopropenylphenol, p-isopropenylphenol, 2-methyl-4-isopropenylphenol and 2-ethyl-4-isopropenylphenol; Examples include arylphenols such as phenylphenol; polyhydroxyphenols such as 4,4′-dihydroxybiphenyl, bisphenol A, resorcinol, hydroquinone, and pyrogallol. Among these phenols, m-cresol and p-cresol are particularly preferable.
These may be used alone or in combination of two or more. Especially, it is preferable to use combining 2 or more types, and it is most preferable to use combining m-cresol and p-cresol.

Examples of the aldehydes include formaldehyde, paraformaldehyde, trioxane, acetaldehyde, propionaldehyde, butyraldehyde, trimethylacetaldehyde, acrolein, crotonaldehyde, cyclohexanealdehyde, furfural, furylacrolein, benzaldehyde, terephthalaldehyde, phenylacetaldehyde, α-phenylpropyl. Aldehyde, β-phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p- Chlorobenzaldehyde, cinnamon Examples include aldehydes. Among these aldehydes, formaldehyde is preferable because of its availability.
These may be used alone or in combination of two or more.

  Examples of the acidic catalyst include hydrochloric acid, sulfuric acid, formic acid, oxalic acid, paratoluenesulfonic acid, and the like, and oxalic acid is preferable.

(A) A component may consist of 1 type of novolak resin, and may consist of 2 or more types of novolak resins. In particular, the sensitivity of the resist composition can be appropriately adjusted by mixing two or more novolak resins.
In the present invention, as the component (A), those containing a novolak resin of the component (A ′) exemplified below are preferable.

[(A ′) component]
In the present invention, the component (A ′) is a mixture of m-cresol / p-cresol = 20/80 to 80/20 in a mixed proportion of m-cresol and p-cresol (molar ratio): It is a novolak resin synthesized using formaldehyde as a condensing agent and having a mass average molecular weight (Mw) (polystyrene conversion standard by gel permeation chromatography) of 1000 to 15000. When the component (A ′) is contained in the component (A), it is suitable for the preparation of a highly sensitive resist composition, and the residual film property of the unexposed area is improved, which is preferable.

In the component (A ′), the ratio (molar ratio) of charging m-cresol and p-cresol is particularly preferably m-cresol / p-cresol = 50/50 to 80/20.
Part of p-cresol used in the synthesis reaction is present in the reaction system as an unreacted product or a binuclear product, and is removed by a fractionation operation for the purpose of cutting low molecular weight substances after the synthesis reaction is completed. It is preferable. In this case, the monomer ratio (molar ratio) of m-cresol structural unit / p-cresol structural unit in the finally obtained novolak resin is preferably 55/45 to 75/25, and preferably 60/40 to 70. / 30 is particularly preferable.

  In the present invention, the component (A) may be used by mixing a plurality of components (A ′) having different proportions of M-cresol and p-cresol and different Mw, and other than the component (A ′) The novolac resin may be contained. However, the total content ratio of the component (A ′) in the component (A) is preferably 50% by mass or more, more preferably 90% by mass or more, and may be 100% by mass. Most preferably, it is 100 mass%.

In addition, as the component (A) of the present invention, a novolak resin having an alkali solubility of preferably 25 to 400 nm / second, more preferably more than 25 nm / second and 400 nm / second or less, further preferably 50 to 400 nm / second. It is preferable to use an alkali-soluble novolak resin comprising When the alkali solubility is within the above range, a positive photoresist composition more suitable for producing a liquid crystal element can be prepared.
In particular, when the alkali solubility is in the range of 50 to 400 nm / second, high sensitivity is obtained, there is little residue in the exposed area, excellent contrast, and high resolution and low verticality of the resist profile under low NA conditions. Is preferable.
In this specification, “alkali solubility” means that a resist layer made of an alkali-soluble novolak resin is provided on a support with a predetermined film thickness (about 0.5 to 2.0 μm), and the resist layer is 2 .38 mass% tetramethylammonium hydroxide (hereinafter referred to as TMAH) in an aqueous solution (about 23 ° C.), the time required for the resist layer to have a film thickness of 0 μm was determined. = Resist layer thickness / Time required for the thickness to become zero]] (nm / second). The resist layer made of an alkali-soluble novolak resin is, for example, dissolved in propylene glycol monomethyl ether acetate (PGMEA) in a novolak resin to form a 20 mass% solution, spin-coated on a 3 inch silicon wafer, and set to 110 ° C. It is formed by performing a heat treatment on the hot plate for 90 seconds.
The “alkali solubility” can be controlled by adjusting the type or ratio of the structural unit constituting the component (A), the Mw of the component (A), and the like.

(A) Mw of the whole component is preferably 1000 or more, more preferably 2000 to 15000, and still more preferably 3000 to 10,000. When the Mw is 1000 or more, it is preferable for making the thickness of the resist film uniform, and the lithography properties of the resist composition are improved.
When the component (A) is composed of two or more novolak resins, the Mw of each novolac resin is not particularly limited, and the component (A) is prepared so that the Mw is 1000 or more as a whole. preferable.

<(C) component>
In the present invention, the component (C) is a naphthoquinonediazide group-containing compound and is a photosensitive component. As the component (C), those conventionally used as a photosensitive component of a positive photoresist composition for producing a liquid crystal element can be used.
Specific examples of the component (C) include, for example, an esterification reaction product (c1) (hereinafter, referred to as a phenolic hydroxyl group-containing compound represented by the following chemical formula (II) and a 1,2-naphthoquinonediazide sulfonic acid compound. (Referred to as component (c1)).

Examples of the 1,2-naphthoquinonediazide sulfonic acid compound include 1,2-naphthoquinonediazide-5-sulfonyl compounds, 1,2-naphthoquinonediazide-4-sulfonyl compounds, and the like, and 1,2-naphthoquinonediazide-5- Sulfonyl compounds are preferred.
The average esterification rate of the component (c1) is preferably 50 to 70%, and more preferably 55 to 65%. When the average esterification rate is 50% or more, film loss after alkali development is suppressed, which is preferable in that the remaining film rate is increased. When the average esterification rate is 70% or less, the storage stability is improved.
The component (c1) is particularly preferred because it is very inexpensive and can prepare a highly sensitive positive photoresist composition.

In addition to the component (c1), other quinonediazide esterified product (c2) (hereinafter referred to as component (c2)) can be used as the component (C).
Examples of the component (c2) include a phenolic hydroxyl group-containing compound represented by the following general formula (III) and a 1,2-naphthoquinone diazide sulfonic acid compound (preferably a 1,2-naphthoquinone diazide-5-sulfonyl compound). Or an esterification reaction product with 1,2-naphthoquinonediazide-4-sulfonyl compound).

  The content ratio of the component (c2) in the component (C) is preferably 50% by mass or less, and particularly preferably 25% by mass or less.

  The content ratio of the component (C) in the positive photoresist composition for manufacturing a liquid crystal element of the present invention is 100 parts by mass in total of the component (A) and the component (B) (described later) blended as necessary. On the other hand, it is preferably within the range of 15 to 40 parts by mass, more preferably within the range of 20 to 35 parts by mass, and even more preferably within the range of 20 to 30 parts by mass. When the content ratio of the component (C) is 15 parts by mass or more, transferability is improved and a resist pattern having a desired shape is easily formed. On the other hand, if it is 40 parts by mass or less, sensitivity and resolution are improved, and generation of a residue after alkali development is suppressed.

<(D) component>
In the present invention, the component (D) is an organic solvent. The positive photoresist composition for producing a liquid crystal device of the present invention can be produced by dissolving a resist material in the component (D).
As the component (D), any resist material can be used as long as it can dissolve each resist material to be used to form a uniform solution. Conventionally, any one of known solvents for resist compositions can be used. Two or more types can be appropriately selected and used.
For example, lactones such as γ-butyrolactone; ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone, 2-heptanone; Monohydric alcohols; compounds having an ester bond, such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, dipropylene glycol monoacetate, monomethyl ether, monoethyl of the polyhydric alcohols or compound having the ester bond Ethers such as ether, monopropyl ether, monobutyl ether and other monoalkyl ethers and monophenyl ether Derivatives of polyhydric alcohols such as compounds having a combination [in these, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) are preferred]; cyclic ethers such as dioxane, methyl lactate Esters such as ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate; anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether , Dibenzyl ether, phenetole, butyl phenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, cymene, mesitylene, etc. Examples include organic solvents.
Among these, PGMEA is most preferable because it is excellent in coating properties and is excellent in the uniformity of the resist film thickness even on a large glass substrate.

(D) A component may be used individually by 1 type, or may be used as a 2 or more types of mixed solvent.
When PGMEA is used as the component (D), it is most preferable to use it as a single solvent.
A solvent other than PGMEA can be used in combination with PGMEA, and examples of the solvent other than PGMEA include ethyl lactate, γ-butyrolactone, propylene glycol monobutyl ether, and the like.
When using ethyl lactate together with PGMEA, the content ratio of ethyl lactate in the positive photoresist composition for liquid crystal element production is preferably 0.1 to 10 times by mass with respect to PGMEA. It is more preferable to mix in 5 times the amount.
When γ-butyrolactone is used in combination with PGMEA, the content ratio of γ-butyrolactone in the positive photoresist composition for liquid crystal element production is preferably 0.01 to 1 times the mass ratio of PGMEA, It is more preferable to mix in an amount of 0.05 to 0.5 times.

  In the present invention, using the component (D), the total content ratio of the component (A) and the component (C) in the positive photoresist composition for manufacturing a liquid crystal element and the component (B) described later is 30 It is preferable to adjust to not more than mass%, more preferably to not more than 28 mass%, and further preferably to not more than 25 mass%. The lower limit is preferably adjusted to 10% by mass or more, more preferably 20% by mass or more. When the content ratio is in the above range, when the resist pattern is formed, the positive photoresist composition for producing a liquid crystal element is ejected in a strip shape from the ejection nozzle and applied onto the support, thereby obtaining good applicability. In addition, since good fluidity is obtained when the film is spun after the coating, it is preferable for forming a resist film with good film thickness uniformity with high yield.

<(E1) component>
In the present invention, the component (E1) is a fluorine-based surfactant having an alkylene oxide chain containing a group represented by the following general formula (E1-0).
By including the component (E1), the uniformity of the film thickness of the resist film is increased.
The component (E1) is a non-PFOA / non-PFOS fluorosurfactant that has been increasingly demanded in recent years.

［式（Ｅ１−０）中、Ｒ^ｆは炭素原子数１〜６のフッ素化アルキル基であり、Ｒ^１１は炭素原子数１〜５のアルキレン基または単結合である。］

[In Formula (E1-0), R ^f represents a fluorinated alkyl group having 1 to 6 carbon atoms, and R ¹¹ represents an alkylene group having 1 to 5 carbon atoms or a single bond. ]

In the formula (E1-0), R ^f is a fluorinated alkyl group having 1 to 6 carbon atoms. Since the number of carbon atoms is 6 or less, it does not correspond to so-called PFOAs or PFOSs.
The fluorinated alkyl group preferably has 1 to 3 carbon atoms, and particularly preferably has 1 or 2 carbon atoms.
The fluorination rate of the fluorinated alkyl group (ratio of fluorine atoms in the alkyl group) is preferably 10 to 100%, more preferably 50 to 100%, and fluorine in which all hydrogen atoms are substituted with fluorine atoms. An alkyl group (perfluoroalkyl group) is most preferred.
R ¹¹ is an alkylene group having 1 to 5 carbon atoms or a single bond, preferably a methylene group, an ethylene group or a propylene group, and most preferably a methylene group.

  As a suitable thing of (E1) component, the compound which has a structure represented by the following general formula (E1-1) is mentioned, for example.

［式（Ｅ１−１）中、Ｒ^ｆは炭素原子数１〜６のフッ素化アルキル基であり、Ｒ^１１およびＲ^１２はそれぞれ独立して炭素原子数１〜５のアルキレン基または単結合であり、Ｒ^１３は水素原子または炭素原子数１〜５のアルキル基であり、ｎ^１は１〜５０であり、ｎ^２は０または１である。］

[In Formula (E1-1), R ^f is a fluorinated alkyl group having 1 to 6 carbon atoms, and R ¹¹ and R ¹² are each independently an alkylene group having 1 to 5 carbon atoms or a single bond. , R ¹³ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, n ¹ is 1 to 50, and n ² is 0 or 1. ]

In the formula (E1-1), R ^f and R ¹¹ are the same as R ^f and R ¹¹ in the formula (E1-0), respectively.
R ¹² is an alkylene group having 1 to 5 carbon atoms or a single bond, preferably a methylene group or ethylene group, and most preferably a methylene group.
R ¹³ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom, a methyl group or an ethyl group, and most preferably a methyl group.
n ¹ is 1 to 50, 1 to 40 are preferred, 3 to 35 is more preferable.
n ² is 0 or 1, and 1 is preferable.

The molecular weight of the component (E1) is preferably 200 to 7000, more preferably 1200 to 6000, and further preferably 1200 to 4500.
When the molecular weight of the component (E1) is 200 to 7000, the uniformity of the resist film thickness is improved.
When the molecular weight of the component (E1) is 1200 to 6000, generation of streak marks after applying the resist composition on the support is suppressed, and the film thickness uniformity of the resist film is further improved.
When the molecular weight of the component (E1) is 1200 to 4500, when the positive photoresist composition is applied on the support, the positive photoresist composition is formed on the edge of the support (hereinafter referred to as “edge bead”). ) Is excellent (edge bead reduction effect). The higher the edge bead reduction effect, the smaller the rising of the positive photoresist composition at the edge portion of the support, the narrower the edge bead width from the edge portion, and the higher the film thickness uniformity of the resist film.

  Preferred specific examples of the component (E1) are illustrated below.

In the present invention, the component (E1) preferably includes a compound having a structure represented by the general formula (E1-1).
Among these, the (E1) component is preferably at least one fluorosurfactant selected from the chemical formulas (E1-1-1) to (E1-1-4), and the edge bead reduction effect is particularly good. Therefore, the chemical formula (E1-1-2) or the chemical formula (E1-1-3) is more preferable, and the chemical formula (E1-1-3) is most preferable.

  Preferable specific examples of the component (E1) include, for example, Polyfox series PF-636, PF-6320, PF-656, and PF-6520 (all trade names, manufactured by Omninova). Among these, PF-656 and PF-6320 are particularly preferable because the edge bead reduction effect is high.

(E1) A component may be used individually by 1 type, or may use 2 or more types together.
The content ratio of the (E1) component in the positive photoresist composition for producing a liquid crystal device of the present invention is based on the total solid content excluding the (D) component, the (E1) component, and the (E2) component from the photoresist composition. It is preferably 0.001 to 5 parts by mass, more preferably 0.001 to 3 parts by mass, and still more preferably 0.01 to 2 parts by mass.
When the content ratio of the component (E1) is at least the lower limit value, the wettability of the positive photoresist composition on the support is improved. On the other hand, if the content ratio of the component (E1) is not more than the upper limit value, the compatibility with other composition components becomes better.

<(E2) component>
In the present invention, it is preferable to further contain a silicon-based surfactant (E2) (hereinafter referred to as (E2) component). By containing the component (E2), it is possible to effectively suppress the occurrence of smears when a positive photoresist composition for producing a liquid crystal element is applied on a support.
Specifically, as the component (E2), a polysiloxane-based surfactant is preferable because the effect of suppressing the occurrence of the above-mentioned haze is more excellent.

In the present specification and claims, the “silicon-based surfactant” refers to a surfactant containing silicon (Si) atoms.
“Polysiloxane-based surfactant” refers to a surfactant having a main chain composed of repeated Si—O bonds.

Among the polysiloxane surfactants, a polyester modified having a repeating unit represented by the following general formula (E2-11) and a repeating unit represented by the following general formula (E2-12) is preferable. And polydialkylsiloxane-based surfactant (E2-1) (hereinafter referred to as (E2-1) component).
By containing the component (E2-1), it is possible to effectively suppress the occurrence of smearing when a photoresist composition is coated on a support, and also a drip mark is generated in a coating method that spins after the central dropping. Can be effectively suppressed, and the uniformity of the film thickness of the resist film is further improved. In addition, it is possible to effectively suppress the occurrence of streak-like marks in the resist coating method using the discharge nozzle method.

［式（Ｅ２−１１）中、Ｒ^１は炭素原子数１〜３の直鎖状または分岐鎖状のアルキル基であり、Ｒ^２は炭素原子数１〜１５の直鎖状または分岐鎖状のアルキル基である。式（Ｅ２−１２）中、Ｒ^１は前記と同じであり、Ｒ^３はポリエステル変性基である。］

[In Formula (E2-11), R ¹ is a linear or branched alkyl group having 1 to 3 carbon atoms, and R ² is a linear or branched chain group having 1 to 15 carbon atoms. It is an alkyl group. In formula (E2-12), R ¹ is the same as described above, and R ³ is a polyester-modified group. ]

In the formula (E2-11), R ¹ is a linear or branched alkyl group having 1 to 3 carbon atoms, preferably a methyl group, an ethyl group, a propyl group, or an isopropyl group, and the methyl group is preferable.
R ² is a linear or branched alkyl group having 1 to 15 carbon atoms, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group , Pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl A linear alkyl group is preferable, and a methyl group, an ethyl group, and a decyl group are more preferable.
In formula (E2-12), R ¹ is the same as described above.
R ³ is a polyester-modified group. “Polyester-modified group” refers to a group containing a polyester group.

The component (E2-1) is not particularly limited as long as it has the two types of repeating units, and may have the two types of repeating units and other repeating units. .
However, in order to sufficiently obtain the effect of containing the component (E2-1), it is preferable that the two types of repeating units are the main component, and at least one terminal of the main chain is represented by the following general formula ( E2-10) is more preferred, and both ends of the main chain are more preferably represented by the following general formula (E2-10).
Here, “main component” means that the ratio of the two kinds of repeating units is 50 mol% or more with respect to the total of all repeating units constituting the component (E2-1), preferably 70 It is at least mol%, more preferably at least 80 mol%, most preferably at least 100 mol%.

［式（Ｅ２−１０）中、Ｒ^１は前記と同じである。］

[In formula (E2-10), R ¹ is the same as defined above. ]

The component (E2-1) preferably has a thermal decomposition point of 130 ° C. or higher, more preferably 170 ° C. or higher.
When the thermal decomposition point is 130 ° C. or higher, the effect of suppressing the occurrence of the above-described haze is improved, and the film thickness uniformity of the resist film is further improved.
The thermal decomposition point indicates a temperature (° C.) at which the mass is decreased, which is measured under a temperature rising condition of 10 ° C./min with a thermal analyzer TG / DTA6200 (product name, manufactured by Seiko Instrument).

  Specific examples of suitable components (E2-1) include BYK-310 and BYK-315 (both are trade names, manufactured by BYK Chemie). Among these, BYK-310 is particularly preferable because it has a high effect of suppressing generation of fogging, dripping marks, and streak marks when a positive photoresist composition is applied on a support.

(E2) A component may be used individually by 1 type, or may use 2 or more types together.
When the (E2) component is contained in the positive photoresist composition for producing a liquid crystal device of the present invention, the content ratio is such that the (D) component, the (E1) component, and the (E2) component are excluded from the photoresist composition. It is preferable that it is 0.001-1 mass part with respect to a total solid, It is more preferable that it is 0.001-0.1 mass part, It is further more preferable that it is 0.1-0.5 mass part. .
When the content ratio of the component (E2) is 0.001 to 1 part by mass, it is possible to effectively and efficiently achieve uniform film thickness of the resist film.
When the content ratio of the component (E2) is 0.001 to 0.1 parts by mass, generation of streak marks can be particularly suppressed.
When the content ratio of the component (E2) is 0.1 to 0.5 parts by mass, it is possible to suppress generation of haze unevenness and dripping marks.

When the positive photoresist composition for producing a liquid crystal device of the present invention contains the (E2) component, the mixing ratio [(E1) / (E2)] of the (E1) component and the (E2) component is ( E1) / (E2) = 1/9 to 9/1 is preferable, 2/8 to 9/1 is more preferable, 4/6 to 8/2 is further preferable, and 5 / 5-7 / 3 is particularly preferred.
When (E1) / (E2) is in the above-mentioned range, the effect of suppressing the occurrence of haze, dripping marks, and streak marks when the photoresist composition is applied onto the support, and the edge bead reduction effect are obtained satisfactorily. It is done. In addition, when the component (E1) is equal to or greater than the proportion of the component (E2), the effect of suppressing generation of haze unevenness and dropping marks is further improved among the above effects.

<(B) component>
In this invention, since the effect of a sensitivity improvement is acquired, it is preferable to contain the phenolic hydroxyl group containing compound (B) of molecular weight 1000 or less further.
(B) The molecular weight of a component is 1000 or less, and it is preferable that it is 200-1000. When the molecular weight of the component (B) is 1000 or less, the effect of improving sensitivity is easily obtained.

  In particular, in the field of manufacturing liquid crystal elements, improvement of throughput is a very big problem, and the resist consumption tends to increase. Therefore, the positive photoresist composition preferably has high sensitivity and is inexpensive, and when the component (B) is used, high sensitivity can be achieved at relatively low cost. In addition, when the component (B) is used, a surface poorly soluble layer is strongly formed in resist pattern formation, so that the amount of unremoved resist film in the unexposed portion is small during alkali development, and development unevenness caused by differences in development time Since generation | occurrence | production is suppressed, it is preferable.

As the component (B), a phenolic hydroxyl group-containing compound having a molecular weight of 1000 or less that has been conventionally used in positive photoresist compositions for producing liquid crystal elements can be appropriately used.
As a specific example of the component (B), for example, a phenolic hydroxyl group-containing compound represented by the following general formula (III) is preferable because the sensitivity can be effectively improved.

［式（ＩＩＩ）中、Ｒ^２１〜Ｒ^２８はそれぞれ独立して水素原子、ハロゲン原子、炭素原子数１〜６のアルキル基、炭素原子数１〜６のアルコキシ基、または炭素原子数３〜６のシクロアルキル基を表し；Ｒ^２９〜Ｒ^３１はそれぞれ独立して水素原子または炭素原子数１〜６のアルキル基を表し；Ｑは水素原子、炭素原子数１〜６のアルキル基、Ｒ^２９と結合して形成する炭素原子数３〜６のシクロアルキル基、または下記一般式（ＩＶ）で表される残基を表し；ａ、ｂは１〜３の整数を表し；ｄは０〜３の整数を表し；ｎは０〜３の整数を表す。］

[In Formula (III), R ^{21 to} R ²⁸ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or 3 to 6 carbon atoms. R ^{29 to} R ³¹ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; Q is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, R ²⁹ and Represents a cycloalkyl group having 3 to 6 carbon atoms formed by bonding, or a residue represented by the following general formula (IV); a and b represent an integer of 1 to 3; d represents 0 to 3 Represents an integer; n represents an integer of 0 to 3; ]

［式（ＩＶ）中、Ｒ^３２およびＲ^３３はそれぞれ独立して水素原子、ハロゲン原子、炭素原子数１〜６のアルキル基、炭素原子数１〜６のアルコキシ基、または炭素原子数３〜６のシクロアルキル基を表し；ｃは１〜３の整数を示す。］

[In Formula (IV), R ³² and R ³³ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or 3 to 6 carbon atoms. C represents an integer of 1 to 3; ]

In the formula (III), R ^{21 to} R ²⁸ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or 3 to 3 carbon atoms. Particularly preferably an alkyl group having 1 to 6 carbon atoms.
In R ^{21 to} R ²⁸ , examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is particularly preferable.
Among the alkyl groups having 1 to 6 carbon atoms, a methyl group, an ethyl group, a propyl group, an n-butyl group, and a tert-butyl group are preferable, and a methyl group is most preferable.
Among the alkoxy groups having 1 to 6 carbon atoms, a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, and a tert-butoxy group are preferable.
R ^{29 to} R ³¹ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and is preferably a hydrogen atom.
a and b each represent an integer of 1 to 3, and is most preferably 1.
d represents an integer of 0 to 3, and is most preferably 1.
n represents an integer of 0 to 3, and is most preferably 0.
Q represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms formed by bonding with R ²⁹ , or a residue represented by the general formula (IV). And most preferably a residue represented by the general formula (IV).

In the formula (IV), R ³² and R ³³ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or 3 to 3 carbon atoms. 6 represents a cycloalkyl group, and is most preferably a hydrogen atom.
Examples of R ³² and R ³³ include the same as R ^{21 to} R ²⁸ .
c represents an integer of 1 to 3, and is most preferably 1.

  Among the above, a phenolic hydroxyl group-containing compound represented by the following chemical formula (I) is particularly preferable because of high sensitivity and high residual film ratio.

(B) A component may be used individually by 1 type or may use 2 or more types together.
In the positive photoresist composition for producing a liquid crystal element of the present invention, when the component (B) is contained, the content is preferably in the range of 1 to 25 parts by mass with respect to 100 parts by mass of the component (A). More preferably, it is in the range of 5 to 20 parts by mass. When the content ratio of the component (B) is 1 part by mass or more, the effect of improving sensitivity and increasing the remaining film ratio is improved. On the other hand, if it is 25 mass parts or less, generation | occurrence | production of the residue in the support body surface after alkali image development will be suppressed. Moreover, since raw material cost can also be suppressed, it is preferable.

<Other ingredients>
The positive photoresist composition for producing a liquid crystal device of the present invention further contains an additive having a miscibility, for example, an adhesion improver for improving the adhesion between the layer comprising the photoresist composition and its lower layer, and halation. An inhibitor, a storage stabilizer, and the like can be appropriately added and contained.

Suitable examples of the adhesion improver include 2- (2-hydroxyethyl) pyridine. When a resist pattern is formed on a metal film such as a Cr film by appropriately including this in the positive photoresist composition for producing a liquid crystal element of the present invention, the adhesion between the layer made of the photoresist composition and the metal film Can be improved effectively.
When the adhesion improver is contained, if the amount is too large, the change over time of the photoresist composition tends to deteriorate, and if it is too small, the effect of improving adhesion cannot be sufficiently obtained. Therefore, the content ratio of the adhesion improver is preferably in the range of 0.1 to 10 parts by mass with respect to the total solid content of the positive photoresist composition for producing a liquid crystal element.

  Antihalation agents include, for example, ultraviolet absorbers for preventing halation, specifically 2,2 ′, 4,4′-tetrahydroxybenzophenone, 4-dimethylamino-2 ′, 4′-dihydroxybenzophenone, 5- Amino-3-methyl-1-phenyl-4- (4-hydroxyphenylazo) pyrazole, 4-dimethylamino-4′-hydroxyazobenzene, 4-diethylamino-4′-ethoxyazobenzene, 4-diethylaminoazobenzene, curcumin, etc. It can be contained as appropriate.

  As described above, the positive photoresist composition for producing a liquid crystal element of the present invention can improve the uniformity of the resist film thickness.

In the LCD manufacturing field, a large substrate (for example, 360 mm × 460 mm or more) is usually used as compared with a silicon wafer used in the semiconductor element manufacturing field. In addition, the surface of the substrate on which the photoresist composition is applied, such as the presence of very macro unevenness on the surface of the substrate for manufacturing the LCD and the distortion of the substrate itself, is the same for LCD manufacturing and semiconductor device manufacturing. It is different from for use. Therefore, the photoresist composition for manufacturing LCDs and the photoresist composition for manufacturing semiconductor devices are technically different.
According to the positive photoresist composition for producing a liquid crystal element according to the present invention, the wettability on the support is excellent. Such an effect is that the support on which the resist film is formed is a large glass square substrate for LCD production or a layer containing molybdenum as a main component such as a molybdenum layer or a molybdenum alloy layer on the surface of the substrate ( Even a support on which a surface layer is formed can be obtained effectively.
Therefore, the positive photoresist composition according to the present invention can be suitably used for producing a liquid crystal element.

In addition, the positive photoresist composition for manufacturing a liquid crystal device of the present invention is applied to the entire coating surface of the support so as to have a final required film thickness by a resist nozzle coating method. Thus, it can be suitably used for a method that does not spin (spinless method), and after coating the photoresist composition on the entire coated surface of the support, the support is spun to adjust the film thickness. It can be suitably used in the method.
In particular, in the latter method, it is possible to suppress the occurrence of streak marks after spinning while suppressing the resist coating amount. Therefore, it is possible to reduce the resist consumption, improve the yield, and reduce the cost.

≪Resist pattern formation method≫
In the resist pattern forming method of the present invention, the step of applying the positive photoresist composition for manufacturing a liquid crystal element on the entire coating surface of the support by moving the discharge nozzle and the support relative to each other; The method includes a step of forming a resist film, a step of exposing the resist film, and a step of forming the resist pattern by alkali development of the resist film.
The resist pattern forming method of the present invention can be performed, for example, as follows.

First, a “coating process” is performed in which the positive photoresist composition for producing a liquid crystal device of the present invention is applied to the entire coated surface of the support.
The support is not particularly limited. For example, a support in which a metal film constituting a gate electrode is formed on an insulating substrate such as a glass substrate and the metal film is a surface layer can be used. .
The surface layer is preferably composed of a metal film containing molybdenum as a main component, such as a molybdenum alloy such as molybdenum tantalum or molybdenum tungsten, or a molybdenum film.
Specifically, for example, a laminated body in which an ITO wiring pattern of about 0.5 μm, an interlayer insulating layer pattern, and a molybdenum film are sequentially formed on a glass substrate can be used as the support.

  The positive photoresist composition for manufacturing a liquid crystal device is applied to the support by a coating method in which spin is performed after the central dropping (hereinafter referred to as a central dropping spin method) or a resist coating method by a discharge nozzle method (hereinafter referred to as a discharge nozzle type coating). Any of the above methods can be used.

  The central dropping spin method can be performed using a known method as appropriate.

The discharge nozzle type coating method can be performed by an apparatus provided with means for relatively moving the discharge nozzle and the support.
The discharge nozzle is not particularly limited as long as the photoresist composition discharged from the discharge nozzle is configured to be applied in a strip shape on the support. For example, a plurality of nozzle holes are arranged in a row. A discharge nozzle having a discharge port and a discharge nozzle having a slit-like discharge port can be used.
As such a device, a coat & spinless type TR63000S (product name; manufactured by Tokyo Ohka Kogyo Co., Ltd.) is known.

Further, in the “coating step”, after applying a positive photoresist composition for manufacturing a liquid crystal device on a support by a discharge nozzle type coating method or the like, a means for adjusting the film thickness by spinning the support is used. You can also.
As a coating apparatus having such means, slit-and-spin type SK-1100G (product name; manufactured by Dainippon Screen Mfg. Co., Ltd.), scan coating with MMN (multi-micro nozzle) + spin type CL1200 (product name: Tokyo) Electron Co., Ltd.), and coat and spin type TR63000F (product name; manufactured by Tokyo Ohka Kogyo Co., Ltd.) are known.

  Particularly in the field of LCD production, the thickness of the resist film formed on the glass substrate is preferably 0.5 to 2.5 μm, and more preferably 1.0 to 2.0 μm. As a means for adjusting the film thickness, it is preferable to use a method in which a positive photoresist composition for producing a liquid crystal element is applied onto a support by the above-described discharge nozzle type coating method, and then the support is spun. .

After applying the positive photoresist composition for manufacturing a liquid crystal element to the entire coated surface of the support as described above, for example, the support coated with the photoresist composition is heated and dried (pre-baked) at about 100 to 140 ° C. Then, a resist film is formed. Thereafter, the resist film is selectively exposed through a desired mask pattern.
As the wavelength at the time of exposure, ghi line (g line, h line, and i line) or i line can be suitably used, and each light source can be used as appropriate.

Thereafter, the resist film after selective exposure is developed using an alkaline developer composed of an alkaline aqueous solution, for example, an aqueous solution of 1 to 10% by mass of tetramethylammonium hydroxide (TMAH).
Examples of the method of bringing the alkali developer into contact with the resist film include a method of depositing liquid from one end of the support to the other end, and support from an alkali developer droplet lower nozzle installed near the center of the support. A method of spreading the alkaline developer over the entire body surface can be used.
And after leaving still for about 50-60 seconds and carrying out alkali image development, a resist pattern is obtained by performing the rinse process which rinses off the alkali developing solution remaining on the resist pattern surface using rinse solutions, such as a pure water.

  Furthermore, when patterning a metal film which is the lower layer of the resist pattern, molybdenum is obtained by immersing in a solution of perchloric acid / cerium nitrate cerium nitrate / water (3: 1: 16 mass ratio) for 10 minutes as an etchant, for example. After selectively etching the film (metal film), the resist pattern is peeled off with a 4% by mass aqueous sodium hydroxide solution, whereby a conductive pattern made of a molybdenum film can be formed on the glass substrate.

Further, when a resist coating method using a discharge nozzle method is used, a resist film can be formed on a support without deteriorating coating uniformity and tact time even when the support size and apparatus size are increased. .
Furthermore, when spin after coating is performed, the generation of streak-like marks can be prevented while suppressing the resist coating amount, which can contribute to a reduction in manufacturing cost.

  Examples of the present invention will be described below, but the scope of the present invention is not limited to these examples.

(Examples 1-9, Comparative Examples 1-2)
The components shown in Table 1 below were mixed and dissolved to prepare a positive photoresist composition for liquid crystal device production. Each abbreviation in Table 1 has the following meaning.

・ Alkali-soluble novolac resin (A)
As the component (A), the following (A1) alone and a mixture in which three types (A1) to (A3) were mixed were used.
In Table 1, in the component (A), (5/2/3) indicating a mixing ratio indicates that (A1) to (A3) are a mixture mixed at a mass ratio of 5/2/3. The amount of component (A) in the photoresist composition was 100 parts by mass.
(A1): For mixed phenols having a charge ratio (molar ratio) of m-cresol and p-cresol of m-cresol / p-cresol = 60/40, formaldehyde is used as a condensing agent, and an oxalic acid catalyst is used. A novolak resin having a Mw of 5000, obtained by subjecting a novolak resin obtained by condensation using a conventional method to fractionation with a water-methanol mixed solvent.
(A2): A novolak resin with Mw 11000, obtained by the same method as (A1).
(A3): obtained by the same method as (A1) except that mixed phenols in which the ratio (molar ratio) of m-cresol and p-cresol was m-cresol / p-cresol = 30/70 was used. Mw 6300 novolac resin.

・ Naphthoquinonediazide group-containing compound (C)
The following (c1) was used as the component (C). The blending amount of (c1) in the photoresist composition was 23 parts by mass with respect to a total of 100 parts by mass of the component (A) and the component (B).
(C1): An esterification reaction product of 1 mol of the compound represented by the following chemical formula (II) and 2.34 mol of 1,2-naphthoquinonediazide-5-sulfonyl chloride.

・ Organic solvent (D)
The following (d1) was used as the component (D). The blending amount of (d1) in the photoresist composition was 430 parts by mass with respect to 100 parts by mass of component (A).
(D1): Propylene glycol monomethyl ether acetate (PGMEA).

・ Fluorine-based surfactant (E1)
The following (e11) and (e12) were used as the component (E1).
The blending amounts of (e11) and (e12) in the photoresist composition shown in Table 1 are values (unit: mass) relative to the total solid content excluding the (D) component, the (E1) component, and the (E2) component. Part).
(E11): Compound represented by the following chemical formula (E1-1-3) (trade name: Polyfox PF-656, manufactured by Omninova).

  (E12): Compound represented by the following chemical formula (E1-1-2) (trade name: Polyfox PF-6320, manufactured by Omninova).

・ Polyester-modified polydialkylsiloxane surfactant (E2)
The following (e2) was used as the component (E2).
The blending amount of (e2) in the photoresist composition shown in Table 1 is a value (unit: parts by mass) relative to the total solid content excluding the (D) component, the (E1) component, and the (E2) component. .
(E2): BYK-310 (trade name, manufactured by Big Chemie).

・ Phenolic hydroxyl group-containing compound (B)
The following (b1) was used as the component (B). The blending amount of (b1) in the photoresist composition was 10 parts by mass with respect to 100 parts by mass of component (A).
(B1): Compound represented by the following chemical formula (I) (molecular weight 376).

Other components 2- (2-hydroxyethyl) pyridine was used as the other components. The blending amount of 2- (2-hydroxyethyl) pyridine in the photoresist composition was 0.25 parts by mass with respect to the total solid content of the photoresist composition.

  The positive photoresist composition for liquid crystal element production obtained above is filtered using a membrane filter having a pore diameter of 0.2 μm to form a “sample”, and a resist film is formed by the following method using the sample. Evaluation of edge beads, evaluation of streak-like marks, evaluation of haze unevenness and dropping marks were performed.

<Formation of resist film>
The sample is applied onto a glass substrate (680 × 880 mm ² ) on which a molybdenum film is formed using a coating apparatus (product name: TR-45, manufactured by Tokyo Ohka Kogyo Co., Ltd.) using a central dropping spin coating method. A coating film having a thickness of 1.5 μm was formed.
Next, the temperature of the hot plate is set to 110 ° C., the first drying is performed for 90 seconds by proximity baking with an interval of about 1 mm, and then the temperature of the hot plate is set to 110 ° C. And a second drying for 120 seconds to form a resist film having a thickness of 1.5 μm.

[Evaluation of edge beads]
The surface of the formed resist film was observed under a sodium lamp, the edge bead width from the edge portion was determined for the edge bead generated at the edge portion of the glass substrate, and the edge bead was evaluated according to the following criteria. The results are shown in Table 2.
A: The edge bead width was 9 mm or less.
○: The edge bead width was more than 9 mm and 12 mm or less.
(Triangle | delta): The edge bead width was more than 12 mm and less than 15 mm.
X: The edge bead width was 15 mm or more.

[Evaluation of streaks]
The surface of the formed resist film was observed under a sodium lamp, and streak marks were evaluated according to the following criteria. The results are shown in Table 2.
○: No streak was observed.
X: Generation of streak-like marks was observed.

[Evaluation of haze and dripping marks]
The surface of the formed resist film was observed under a sodium lamp, and the haze and dropping marks were evaluated according to the following criteria. The results are shown in Table 2.
○: Generation of haze unevenness and drip marks were not observed.
(Triangle | delta): Although generation | occurrence | production of haze unevenness and dripping trace was recognized slightly, it was a grade which is satisfactory practically.
X: Generation of haze and dripping marks were observed.

As is clear from the results of Table 2, Examples 1 to 9 according to the present invention containing a fluorosurfactant (E1) have a better edge bead width reduction effect than Comparative Example 1, and resists It was confirmed that the film thickness was highly uniform. In particular, Examples 1 to 3 and 6 to 8 were confirmed to have high uniformity of the resist film thickness.
In Examples 1 to 9, neither PFOAs nor PFOSs are used.

In addition, since Examples 1 to 9 show no generation of streak-like marks, and Examples 1 to 5 and 8 show no generation of haze and dripping marks, their coating properties are the same as in the past. It was confirmed that it was excellent.
In Comparative Example 2, since the occurrence of streak-like marks was observed, the evaluation of edge beats and evaluation of haze unevenness and dripping marks could not be performed.

Claims (10)

Fluorine-based surfactant having an alkali-soluble novolak resin (A), a naphthoquinonediazide group-containing compound (C), an organic solvent (D), and an alkylene oxide chain containing a group represented by the following general formula (E1-0) ( A positive photoresist composition for producing a liquid crystal device, comprising E1).

Wherein (E1-0), ^{R f} is a fluorinated alkyl group having 1 to 6 carbon ^{atoms, R 11} is an alkylene group having 1 to 5 carbon atoms. ] The positive photoresist composition for producing a liquid crystal element according to claim 1, wherein the fluorine-based surfactant (E1) contains a compound having a structure represented by the following general formula (E1-1).

Wherein (E1-1), ^{R f} is a fluorinated alkyl group having 1 to 6 carbon ^{atoms, R 11} is an alkylene group having 1 to 5 carbon atoms, ^{R 12} is carbon atom number of 1 to 5 is an alkylene group or a single bond, R ¹³ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, n ¹ is 1 to 50, and n ² is 0 or 1. ]   The positive photoresist composition for producing a liquid crystal device according to claim 1, further comprising a silicon-based surfactant (E2). Alkali-soluble novolak resin (A), the naphthoquinone diazide group-containing compound (C), organic solvent (D), a fluorine-based surfactant having an alkylene oxide chain containing a group represented by the following general formula (E1-0) ( A positive photoresist composition for producing a liquid crystal device , comprising E1) and a silicon-based surfactant (E2) .

[In Formula (E1-0), R ^f represents a fluorinated alkyl group having 1 to 6 carbon atoms, and R ¹¹ represents an alkylene group having 1 to 5 carbon atoms or a single bond. ] The positive photoresist composition for manufacturing a liquid crystal element according to claim 4, wherein the fluorine-based surfactant (E1) contains a compound having a structure represented by the following general formula (E1-1).

[In Formula (E1-1), R ^f is a fluorinated alkyl group having 1 to 6 carbon atoms, and R ¹¹ and R ¹² are each independently an alkylene group having 1 to 5 carbon atoms or a single bond. , R ¹³ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, n ¹ is 1 to 50, and n ² is 0 or 1. ] The positive photoresist composition for producing a liquid crystal device according to any one of claims 3 to 5, wherein the silicon-based surfactant (E2) is a polysiloxane-based surfactant. Polyester-modified polydialkylsiloxane-based surfactant in which the polysiloxane surfactant has a repeating unit represented by the following general formula (E2-11) and a repeating unit represented by the following general formula (E2-12) The positive photoresist composition for manufacturing a liquid crystal device according to claim 6 , comprising an agent (E2-1).

[In Formula (E2-11), R ¹ is a linear or branched alkyl group having 1 to 3 carbon atoms, and R ² is a linear or branched chain group having 1 to 15 carbon atoms. It is an alkyl group. In formula (E2-12), R ¹ is the same as described above, and R ³ is a polyester-modified group. ] The mixing ratio [(E1) / (E2)] of the fluorosurfactant (E1) and the silicon surfactant (E2) is (E1) / (E2) = 1/9 to 9 in mass ratio. liquid crystal device for manufacturing positive photoresist composition according to any one of claims 3-7 is / 1. Furthermore, the positive photoresist composition for liquid crystal element manufacture as described in any one of Claims 1-8 containing the phenolic hydroxyl group containing compound (B) of molecular weight 1000 or less. The step of applying the positive photoresist composition for manufacturing a liquid crystal device according to any one of claims 1 to 9 to the entire coating surface of the support by relatively moving the discharge nozzle and the support, the support A resist pattern forming method comprising a step of forming a resist film on a body, a step of exposing the resist film, and a step of forming the resist film by alkali development of the resist film.