KR100934140B1 - Positive photoresist composition and method of forming resist pattern for liquid crystal device manufacturing - Google Patents

Abstract

Fluorine-type surfactant which has the alkylene oxide chain containing group represented by alkali-soluble novolak resin (A), a naphthoquinone diazide group containing compound (C), an organic solvent (D), and the following general formula (E1-0). Positive photoresist composition for liquid crystal element manufacture containing (E1).

[Formula 1]

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

Description

POSITIVE RESIST COMPOSITION FOR PRODUCING A LIQUID CRYSTAL ELEMENT AND RESIST PATTERN FORMATION METHOD}

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

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

Conventionally, in the LCD manufacturing field, the coating method which spins after center dropping is used abundantly as the coating method of a positive type photoresist composition (for example, refer nonpatent literature 1).

Moreover, especially in the field of LCD manufacturing, a board | substrate tends to become large year by year. The application method of spin after the center dropping is, for example, when a large substrate of 1 m square class is used, the amount of positive photoresist composition scattered and discarded during rotation (spinning) is significantly increased, It has become difficult to meet the requirements other than the uniformity of the film thickness of a resist film, such as a crack of a board | substrate and the problem of ensuring tact time.

From such a present situation, as a method of applying a new positive photoresist composition applicable to a large substrate after the fourth generation substrate (680 mm x 880 mm), particularly after the fifth generation substrate (about 1000 mm x 1200 mm to 1280 mm x 1400 mm), The resist coating method by a discharge nozzle type is proposed.

The resist coating method by a discharge nozzle type is a method of apply | coating positive type photoresist composition to the whole surface of the application surface of a support body by moving a discharge nozzle and a support body relatively.

In the resist coating method using a discharge nozzle type, for example, a discharge nozzle capable of discharging a positive photoresist composition in a strip form having a discharge or slit discharge port in which a plurality of nozzle holes are arranged in a column shape is formed. A method of use is proposed. Moreover, after apply | coating positive type photoresist composition to the whole surface of the application | coating surface of a support body by the discharge nozzle type, the method of adjusting the film thickness by spinning the said support body is also proposed.

In addition, a positive photo-containing compound containing a surfactant such as perfluorooctanoic acid (PFOA), perfluorooctane sulfonic acid (PFOS), or the like as a means for improving the applicability when applying on a support such as a substrate. Although a resist composition is known, in recent years, the demand for non-PFOA formation and non-PFOSization is increasing, and conversion of non-PFOA and non-PFOS into surfactant is desired.

Non-Patent Document 1: Electric Journal (E1ectronic Journal) August 2002, pages 121-123

In recent years, enlargement of the board | substrate used as a support body is advanced. In the above support, while improving the resist pattern shape and various lithography characteristics are required, in order to perform desired patterning with good precision, it is important to make the film thickness of the resist film uniform over the entire surface of the support. One.

However, in the conventional positive photoresist composition, for example, swelling of the resist composition (hereinafter referred to as "edge bead") occurs at the edge portion of the support, so that the film thickness of the resist film tends to be uneven. have.

This invention is made | formed in view of the said situation, and makes it a subject to provide the positive photoresist composition for liquid crystal element manufacture, and the resist pattern formation method which can improve the uniformity of the film thickness of a resist film.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining, the present inventors discovered that the said subject was solved by using the positive photoresist composition which mix | blended the specific surfactant, and completed this invention.

That is, 1st aspect of this invention is alkali-soluble novolak resin (A), a naphthoquinone diazide group containing compound (C), an organic solvent (D), and the following general formula (E1-0). It is a positive type photoresist composition for liquid crystal element manufacture which contains the fluorine-type surfactant (E1) which has the alkylene oxide chain containing the group shown.

[Formula 1]

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

Moreover, the 2nd aspect of this invention is a process of apply | coating the positive photoresist composition for liquid crystal element manufacture of a said 1st aspect to the whole surface of the application | coating surface of a support body by moving a discharge nozzle and a support body relatively on the said support body. A resist pattern forming method includes a step of forming a resist film, a step of exposing the resist film, and a step of alkali developing the resist film to form a resist pattern.

In addition, in this specification and a claim, a "structural unit" means the monomer unit (monomer unit) which comprises a resin component (polymer, a copolymer).

"Alkyl group" shall contain a linear, branched, and cyclic monovalent saturated hydrocarbon group unless otherwise specified.

"Alkylene group" shall contain a divalent saturated hydrocarbon group of linear, branched, and cyclic unless otherwise specified.

"Lower alkyl group" means an alkyl group having 1 to 5 carbon atoms.

"Exposure" is not only radiation but also radiation such as ArF excimer laser, KrF excimer laser, F ₂ excimer laser, EUV (extreme ultraviolet), VUV (vacuum ultraviolet), EB (electron beam), X-ray, soft X-ray It is assumed that the concept includes the whole survey.

The "coated surface of the support body" refers to the region to which the positive photoresist composition should be applied in the support, and generally means the entire surface of one surface of the support.

According to the present invention, it is possible to provide a positive photoresist composition for producing a liquid crystal element and a method of forming a resist pattern capable of improving the uniformity of the film thickness of a resist film.

<< positive photoresist composition for liquid crystal element manufacturing >>

Positive type photoresist composition for liquid crystal element manufacture of this invention is alkali-soluble novolak resin (A) (henceforth (A) component.), A naphthoquinone diazide group containing compound (C) (hereinafter, (C) Component)), 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, it is called (E1) component.).

<(A) component>

In this invention, (A) component is alkali-soluble novolak resin, It can select arbitrarily and can use from what can be normally used as a film formation material in positive type photoresist composition.

As a specific example of (A) component, the novolak resin etc. which are obtained by making phenols and aldehydes react under an acidic catalyst are mentioned.

As said phenols, For example, Phenol; cresols such as m-cresol, p-cresol and o-cresol; Xylenols such as 2,3-xylenol, 2,5-xylenol, 3,5-xylenol and 3,4-xylenol; m-ethylphenol, p-ethylphenol, o-ethylphenol, 2,3,5-trimethylphenol, 2,3,5-triethylphenol, 4-tert-butylphenol, 3-tert-butylphenol, 2- alkyl phenols such as tert-butylphenol, 2-tert-butyl-4-methylphenol and 2-tert-butyl-5-methylphenol; alkoxy phenols such as p-methoxyphenol, m-methoxyphenol, p-ethoxyphenol, m-ethoxyphenol, p-propoxyphenol and m-propoxyphenol; isopropenylphenols such as o-isopropenylphenol, p-isopropenylphenol, 2-methyl-4-isopropenylphenol and 2-ethyl-4-isopropenylphenol; Aryl phenols such as phenyl phenol; And 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 independently or may be used in combination of 2 or more type. Especially, it is preferable to use in combination of 2 or more type, and it is most preferable to use in combination m-cresol and p-cresol.

As the aldehydes, for example, formaldehyde, paraformaldehyde, trioxane, acetaldehyde, propionaldehyde, butylaldehyde, trimethylacetaldehyde, acrolein, crotonaldehyde, cyclohexanealdehyde, furfural, furyl aldehyde, benzfur , Terephthalaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p- Methyl benzaldehyde, o-chloro benzaldehyde, m-chloro benzaldehyde, p-chloro benzaldehyde, cinnamic aldehyde, etc. are mentioned. Among these aldehydes, formaldehyde is preferable from the availability.

These may be used independently or may be used in combination of 2 or more type.

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 be 1 type of novolak resin, and may be 2 or more types of novolak resin. In particular, the sensitivity of the resist composition can be appropriately adjusted by mixing two or more kinds of novolak resins.

In this invention, it is preferable to contain the novolak resin of (A ') component illustrated below as (A) component.

[(A ') component]

In the present invention, the component (A ') is condensed formaldehyde with respect to the mixed phenols in which the ratio (molar ratio) of m-cresol and p-cresol is m-cresol / p-cresol = 20/80 to 80/20. The mass mean molecular weight (Mw) (polystyrene conversion basis by gel permeation chromatography) synthesize | combined using as a agent is 1000-15000 novolak resin. When (A ') component is contained in (A) component, it is suitable for preparation of a highly sensitive resist composition, and since the residual film property of an unexposed part improves, it is preferable.

In the component (A '), the addition ratio (molar ratio) of m-cresol and p-cresol is particularly preferably m-cresol / p-cresol = 50/50 to 80/20.

In addition, it is preferable that a part of p-cresol used for the synthesis reaction exists in a reaction system as an unreacted substance or binary nucleus substance, and is removed by the fractionation operation performed for the purpose of the cut of a low molecular weight body after completion | finish of a synthesis reaction. In this case, the monomer ratio (molar ratio) of the m-cresol structural unit / p-cresol structural unit in the finally obtained novolak resin is preferably 55/45 to 75/25, and is 60/40 to 70/30. It is especially preferable.

In the present invention, the component (A) may be used by mixing a plurality of (A ') components having different amounts of M-cresol and p-cresol and different Mw, and novolacs other than the component (A'). You may contain resin. However, it is preferable that the content rate of the sum total of (A ') component in (A) component is 50 mass% or more, It is more preferable that it is 90 mass% or more, 100 mass% may be sufficient as it. Most preferably 100% by mass.

Moreover, as (A) component of this invention, alkali solubility becomes like this. Preferably it is 25-400 nm / sec, More preferably, it is the furnace which is more than 25 nm / sec. 400 nm / sec or less, More preferably, it is the range of 50-400 nm / sec. Preference is given to using alkali-soluble novolac resins composed of volac resins. If alkali solubility is the said range, the positive photoresist composition more preferable for liquid crystal element manufacture can be prepared.

In particular, when the alkali solubility is in the range of 50 to 400 nm / sec, high sensitivity is obtained, there are few residues in the exposed portion, and the contrast is excellent, and the high resolution in the low NA condition and the perpendicularity of the resist profile are excellent. desirable.

In addition, in this specification, "alkali solubility" means the resist layer which consists of alkali-soluble novolak resin is formed on a support body by predetermined | prescribed film thickness (about 0.5-2.0 micrometers), and the said resist layer is 2.38 mass% tetramethyl. It is immersed in an aqueous solution of ammonium hydroxide (hereinafter referred to as TMAH) (about 23 ° C), and the time required until the film thickness of the resist layer becomes 0 µm is obtained, and the following formula [alkali solubility = of the resist layer Film thickness / time required for the film thickness to become zero]. The resist layer made of an alkali-soluble novolak resin is, for example, dissolved in a propylene glycol monomethyl ether acetate (PGMEA) to form a solution at a concentration of 20% by mass, and spin-coated onto a 3-inch silicon wafer. It is formed by performing a heat treatment for 90 seconds on a hot plate set at 110 ° C.

Said "alkali solubility" can be controlled by adjusting the kind of the structural unit which comprises (A) component, its ratio, Mw of (A) component, etc.

It is preferable that it is 1000 or more, as for Mw of the whole (A) component, it is more preferable that it is 2000-15000, and it is still more preferable that it is 3000-10000. When Mw is 1000 or more, it is preferable in making the film thickness of a resist film uniform, and the lithographic characteristic of a resist composition improves.

When (A) component consists of 2 or more types of novolak resin, Mw of each novolak resin is not specifically limited, It is preferable to prepare so that Mw may be 1000 or more as the whole (A) component.

<(C) component>

In this invention, (C) component is a naphthoquinone diazide group containing compound and is a photosensitive component. As the component (C), one that has conventionally been used as the photosensitive component of the positive photoresist composition for liquid crystal device production can be used.

As a specific example of (C) component, the esterification reaction product (c1) of a phenolic hydroxyl group containing compound represented by following General formula (II), and 1,2-naphthoquinone diazide sulfonic-acid compound (following, (c1) component.) are mentioned as a preferable thing.

[Formula 2]

Examples of the 1,2-naphthoquinone diazide sulfonic acid compound include 1,2-naphthoquinone diazide-5-sulfonyl compound and 1,2-naphthoquinone diazide-4-sulfonyl compound. And 1,2-naphthoquinone diazide-5-sulfonyl compound is preferable.

It is preferable that it is 50 to 70%, and, as for the average esterification rate of the said (c1) component, it is more preferable that it is 55 to 65%. When the said average esterification rate is 50% or more, the film | membrane reduction after alkali image development is suppressed and it is preferable at the point which a residual film rate becomes high. When the average esterification rate is 70% or less, storage stability is improved.

The said (c1) component is especially preferable at the point which can prepare a highly sensitive positive photoresist composition at very low cost.

Moreover, other quinonediazide ester cargo (c2) (henceforth a component (c2)) can be used as (C) component other than the said (c1) component.

As the component (c2), for example, a phenolic hydroxyl group-containing compound represented by General Formula (III) described later and a 1,2-naphthoquinone diazide sulfonic acid compound (preferably 1,2-naphthoquinone Esterification reaction products of diazide-5-sulfonyl compounds or 1,2-naphthoquinone diazide-4-sulfonyl compounds).

It is preferable that it is 50 mass% or less, and, as for the content rate of (c2) component in (C) component, it is especially preferable that it is 25 mass% or less.

The content rate of (C) component in the positive photoresist composition for liquid crystal element manufacture of this invention is 15-15 with respect to 100 mass parts of total amounts of (A) component and (B) component (after-mentioned) mix | blended as needed. It is preferable to exist in the range of 40 mass parts, It is more preferable to exist in the range of 20-35 mass parts, It is still more preferable to exist in the range of 20-30 mass parts. When the content ratio of the component (C) is 15 parts by mass or more, the transferability is improved, and a resist pattern having a desired shape is easily formed. On the other hand, if it is 40 mass parts or less, a sensitivity and resolution will improve and the generation of the residue after an alkali image development process will be suppressed.

<(D) component>

In the present invention, the component (D) is an organic solvent. The positive photoresist composition for liquid crystal device production of the present invention can be produced by dissolving a resist material in the component (D).

As (D) component, what is necessary is just to melt | dissolve each resist material to be used and to make it a uniform solution, and conventionally selects arbitrary 1 type (s) or 2 or more types suitably from the well-known as the solvent of a resist composition, and is used. Can be.

For example, lactones, such as (gamma) -butyrolactone; Ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone, and 2-heptanone; Polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol and dipropylene glycol; Monomethyl ether, monoethyl ether, Derivatives of polyhydric alcohols such as monoalkyl ethers such as monopropyl ether and monobutyl ether or compounds having ether bonds such as monophenyl ether [In these, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME) is preferable]; Cyclic ethers such as dioxane; Esters such as methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate and ethyl ethoxypropionate; Anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phentol, butyl phenyl ether, ethyl benzene, diethyl benzene, pentyl benzene, isopropyl benzene, toluene, xylene, cymene, mesh Aromatic organic solvents, such as styrene, etc. are mentioned.

Among these, PGMEA is most preferable at the point which is excellent in applicability | paintability and the uniformity of the film thickness of a resist film also on a large glass substrate.

(D) component may be used individually by 1 type, or may be used as 2 or more types of mixed solvents.

When using PGMEA as (D) component, it is most preferable to use it as 1 type of independent solvent.

A solvent other than PGMEA may be used together with PGMEA. Examples of the solvent other than PGMEA include ethyl lactate, γ-butyrolactone, and propylene glycol monobutyl ether.

When ethyl lactate is used together with PGMEA, it is preferable to mix | blend the content rate of ethyl lactate in the positive photoresist composition for liquid crystal element manufacture in 0.1-10 times mass ratio with respect to PGMEA, and mix | blend in 1-5 times amount It is more preferable.

When using gamma -butyrolactone together with PGMEA, it is preferable to mix | blend the content rate of gamma-butyrolactone in the positive photoresist composition for liquid crystal element manufacture in 0.01-1 times by mass ratio with respect to PGMEA, and 0.05 It is more preferable to mix | blend in -0.5 times.

In this invention, 30 mass of the content rate of the sum total of (A) component and (C) component in the positive photoresist composition for liquid crystal element manufacture, and (B) component mentioned later using (D) component is used. It is preferable to prepare in% or less, It is more preferable to prepare at 28 mass% or less, It is further more preferable to prepare at 25 mass% or less. It is preferable to prepare a lower limit in 10 mass% or more, and it is more preferable to prepare in 20 mass% or more. When the said content ratio is the said range, in forming a resist pattern, when apply | coating the positive photoresist composition for liquid crystal element manufacture for strip | belt shape from a discharge nozzle, and apply | coating on a support body, favorable applicability | paintability will be obtained. Moreover, since favorable fluidity | liquidity is obtained when it spins after the said application | coating, it is preferable in forming a resist film with favorable uniformity of film thickness in a favorable 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 containing (E1) component, the uniformity of the film thickness of a resist film becomes high. Moreover, (E1) component is fluorine-type surfactant of non-PFOAs and non-PFOSs which are increasing in demand recently.

[Formula 3]

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

In said formula (E1-0), R <^1> is a C1-C6 fluorinated alkyl group. Since the number of carbon atoms is 6 or less, they do not correspond to so-called PFOA or PFOS. As said fluorinated alkyl group, it is preferable that it is C1-C3, and it is especially preferable that it is C1-C2.

Further, the fluorination rate (ratio of fluorine atoms in the alkyl group) of the fluorinated alkyl group is preferably 10 to 100%, more preferably 50 to 100%, and a fluorinated alkyl group in which all of the hydrogen atoms are replaced with fluorine atoms (perfluoro Alkyl groups) are most preferred.

R <^11> is a C1-C5 alkylene group or a single bond, A methylene group, an ethylene group, and a propylene group are preferable, and a methylene group is the most preferable.

As a preferable thing of (E1) component, the compound which has a structure represented by following General formula (E1-1) is mentioned, for example. It is preferable that both ends of this compound are OH groups.

[Formula 4]

[In formula (E1-1), ^Rf is a C1-C6 fluorinated alkyl group; 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 1-50; n ² is 0 or 1]

The formula (E1-1) of, R ^f, and R ¹¹ are, respectively, the same meaning as R ^f, and R ¹¹ in the formula (E1-0).

R <^12> is a C1-C5 alkylene group or a single bond, A methylene group and an ethylene group are preferable, and a methylene group is the most preferable.

R ¹³ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom, a methyl group, an ethyl group, and most preferably a methyl group.

n <^1> is 1-50, 1-40 are preferable and 3-35 are more preferable.

n ² is 0 or 1, and 1 is preferable.

It is preferable that the molecular weight of (E1) component is 200-7000, It is more preferable that it is 1200-6000, It is further more preferable that it is 1200-4500.

If the molecular weight of the component (E1) is 200 to 7000, the uniformity of the film thickness of the resist film is improved.

When the molecular weight of (E1) component is 1200-6000, generation | occurrence | production of the stripe trace after apply | coating a resist composition on a support body is suppressed, and the uniformity of the film thickness of a resist film further improves.

When the molecular weight of (E1) component is 1200-4500, when the positive photoresist composition is apply | coated on a support body, swelling of the positive photoresist composition which generate | occur | produces in the edge part of a support body (henceforth "edge bead"). ) Is excellent in the effect (edge bead reduction effect). As the edge bead reducing effect is higher, the swelling of the positive photoresist composition at the edge portion of the support is smaller, the width of the edge bead from the edge portion can be narrowed, and the uniformity of the film thickness of the resist film is increased. .

Preferable specific examples of the component (E1) are shown below.

[Formula 5]

In this invention, it is preferable to contain the compound which has a structure represented by said general formula (E1-1) as (E1) component.

Among the above, the component (E1) is preferably at least one fluorine-based surfactant selected from formulas (E1-1-1) to (E1-1-4), and the formula (E1) is particularly advantageous in that the edge bead reducing effect is particularly good. -1-2) or general formula (E1-1-3) are more preferable, and general formula (E1-1-3) is the most preferable.

As a preferable specific example of (E1) component, PF-636, PF-6320, PF-656, PF-6520 (all are brand names, the product made by Ohmova Corporation) etc. of the polyfox series are mentioned, for example. Among these, PF-656 and PF-6320 are especially preferable because they have high edge bead reduction effect.

A component (E1) may be used individually by 1 type, or may use 2 or more types together.

The content rate of (E1) component in the positive photoresist composition for liquid crystal element manufacture of this invention is the total solid except the (D) component, (E1) component, and (E2) component (described later) from the said photoresist composition. It is preferable that it is 0.001-5 mass parts with respect to it, It is more preferable that it is 0.001-3 mass parts, It is still more preferable that it is 0.01-2 mass parts.

When the content ratio of the component (E1) is at least the lower limit, the wettability of the positive photoresist composition on the support is improved. On the other hand, compatibility with another composition component becomes it favorable that the content rate of (E1) component is below an upper limit.

<(E2) component>

In this invention, it is also preferable to contain silicone type surfactant (E2) (henceforth a component (E2).). By containing (E2) component, generation | occurrence | production of the nonuniform hazes in apply | coating the positive photoresist composition for liquid crystal element manufacture on a support body can be suppressed effectively.

Specifically as the component (E2), a polysiloxane-based surfactant is preferable because the effect of suppressing the occurrence of the above-mentioned nonuniform haze is further excellent.

In this specification and a claim, "silicone surfactant" means surfactant containing a silicon (Si) atom.

"Polysiloxane type surfactant" means surfactant which has a principal chain which consists of repetition of a Si-0 bond.

Among the polysiloxane surfactants, polyester-modified polydialkylsiloxane surfactants having a repeating unit represented by the following General Formula (E2-11) and a repeating unit represented by the following General Formula (E2-12) (E2- 1) (Hereinafter, it is called (E2-1) component.).

By containing (E2-1) component, generation | occurrence | production of the nonuniform haze at the time of apply | coating a photoresist composition on a support body can be suppressed effectively. Moreover, in the coating method which spins after center dripping, it can suppress that a drip trace arises effectively, and the uniformity of the film thickness of a resist film improves more. Moreover, in the resist coating method by a discharge nozzle type, generation | occurrence | production of a stripe trace can be effectively suppressed.

[Formula 6]

[In formula (E2-11), R <^1> is a C1-C3 linear or branched alkyl group, R <^2> is a C1-C15 linear or branched alkyl group. ; R <^1> is synonymous with the above in formula (E2-12), and R <^3> is a polyester modified group.]

In said formula (E2-11), R <^1> is a C1-C3 linear or branched alkyl group, A methyl group, an ethyl group, a propyl group, and an isopropyl group are preferable, and a 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 The group, a nonadecyl group, an eicosyl group, etc. are mentioned, A linear alkyl group is preferable among these, A methyl group, an ethyl group, and a decyl group are more preferable.

In said formula (E2-12), R <^1> is synonymous with the above.

R ³ is a polyester modifier. "Polyester-modified group" means group containing a polyester group.

The component (E2-1) is not particularly limited as long as it has the two kinds of repeating units, and may have the two kinds of repeating units and other repeating units.

However, in order to fully acquire the effect by containing (E2-1) component, it is preferable to have the said 2 types of repeating unit as a main component, and at least one terminal of a principal chain is following General formula (E2-10) It is more preferable to represent, and it is still more preferable that both terminals of a main chain are represented with the following general formula (E2-10).

Here, "main component" means that the ratio of the said 2 types of repeating units is 50 mol% or more with respect to the sum total of all the repeating units which comprise (E2-1) component, Preferably it is 70 mol% or more, More preferably, it is 80 mol% or more, Most preferably, it is 100 mol%.

[Formula 7]

[In formula (E2-10), R ¹ has the same meaning as described above.]

As a component (E2-1), it is preferable that a thermal decomposition point is 130 degreeC or more, and it is more preferable that it is 170 degreeC or more.

If a thermal decomposition point is 130 degreeC or more, the said effect of suppressing occurrence of nonuniform haze improves, and the uniformity of the film thickness of a resist film improves more.

The thermal decomposition point represents the temperature (° C) at which the mass is reduced, measured under a temperature raising condition of 10 ° C / min with a thermal analyzer TG / DTA6200 (product name, manufactured by Seiko Instrument).

As a preferable specific example of (E2-1) component, BYK-310 (polyester-modified polydimethylsiloxane solution), BYK-315 (polyester-modified polymethylalkylsiloxane solution) ((all brand names, the product made by BICKEMY Corporation), etc. Among these, BYK-310 is particularly preferable because of its high effect of suppressing the occurrence of uneven haze, dripping traces and streaked traces when the positive photoresist composition is applied onto a support.

A component (E2) may be used individually by 1 type, or may use 2 or more types together.

In the positive photoresist composition for liquid crystal device production of the present invention, when the component (E2) is contained, the content ratio is the total solid content except the component (D), the component (E1), and the component (E2) from the photoresist composition. It is preferable that it is 0.001-1 mass part with respect to, and it is more preferable that it is 0.001-0.5 mass part. Furthermore, it is more preferable that it is 0.001-0.1 mass part, and it is still more preferable that it is 0.1-0.5 mass part. If the content ratio of (E2) component is 0.001-1 mass part, the uniformity of the film thickness of a resist film will be achieved effectively and efficiently. can do.

When the content ratio of the component (E2) is 0.001 to 0.1 parts by mass, the occurrence of streaked marks can be particularly suppressed.

When the content ratio of the component (E2) is 0.1 to 0.5 parts by mass, in particular, occurrence of nonuniform haze and dripping traces can be suppressed.

In the positive photoresist composition for liquid crystal device production of the present invention, when the component (E2) is contained, the mixing ratio [(E1) / (E2)] of the component (E1) and the component (E2) is (E1) by mass ratio. It is preferable that it is / (E2) = 1 / 9-9 / 1/1, It is more preferable that it is 2 / 8-9 / 1, It is still more preferable that it is 4 / 6-8 / 2, 5 / 5-7 / 3 Is particularly preferred.

When (E1) / (E2) is the said range, the effect which suppresses generation | occurrence | production of the nonuniform haze, the dripping trace, and the stripe-shaped trace at the time of apply | coating a photoresist composition on a support body, and the edge bead reduction effect are favorable. Obtained. Moreover, if (E1) component is more than the ratio equivalent to (E2) component, the effect of suppressing generation | occurrence | production of a nonuniform haze and dripping traces further improves among the said 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.

The molecular weight of (B) component is 1000 or less, and it is preferable that it is 200-1000.

If the molecular weight of (B) component is 1000 or less, the effect of a sensitivity improvement will become easy to be acquired.

In particular, in the field of liquid crystal element manufacture, the improvement of throughput is a very big problem, and the resist consumption is likely to increase. Therefore, in a positive photoresist composition, it is preferable that it is highly sensitive and inexpensive, and using said component (B) can achieve high sensitivity relatively inexpensively. In addition, when the component (B) is used, the surface poorly soluble layer is strongly formed in forming the resist pattern, so that the amount of film reduction of the resist film of the unexposed portion during alkali development is small, and the occurrence of phenomenon unevenness that occurs due to the difference in development time This is preferable at the point which is suppressed.

As the component (B), a phenolic hydroxyl group-containing compound having a molecular weight of 1,000 or less that is conventionally used for a positive photoresist composition for liquid crystal device production can be appropriately used.

As a specific example of (B) component, the phenolic hydroxyl group containing compound represented by following General formula (III) is mentioned as a preferable thing at the point which can improve a sensitivity effectively.

[Formula 8]

[In formula (III), R <^21> -R <^28> is respectively independently a hydrogen atom, a halogen atom, a C1-C6 alkyl group, a C1-C6 alkoxy group, or C3-C6 cyclo An alkyl group; R ²⁹ to R ³¹ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; 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 to R ²⁹ , or a residue represented by the following General Formula (IV); a and b represent the integer of 1-3; d represents an integer of 0 to 3; n represents an integer of 0 to 3; When a, b or d is 3, R ²³ , R ²⁶ or R ²⁸ are not present, respectively.]

[Formula 9]

[In formula (IV), R <^32> and R <^33> is respectively independently a hydrogen atom, a halogen atom, a C1-C6 alkyl group, a C1-C6 alkoxy group, or C3-C6 cyclo. An alkyl group; c represents an integer of 1 to 3.]

In said formula (III), R <^21> -R <^28> is respectively independently a hydrogen atom, a halogen atom, a C1-C6 alkyl group, a C1-C6 alkoxy group, or C3-C6 cyclo An alkyl group is shown and it is especially preferable that it is a C1-C6 alkyl group.

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 particularly preferably a fluorine atom.

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 preferred.

Among the alkoxy groups having 1 to 6 carbon atoms, methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy and tert-butoxy groups are preferred.

R ²⁹ to R ³¹ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and are preferably a hydrogen atom.

a and b represent the integer of 1-3 and it is most preferable that it is 1;

d represents the integer of 0-3 and it is most preferable that it is 1.

n represents the integer of 0-3 and it is most preferable that it is 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 to R ²⁹ , or a residue represented by the general formula (IV), and the general formula (IV) It is most preferable that it is a residue shown by these.

In said formula (IV), R <^32> and R <^33> is respectively independently a hydrogen atom, a halogen atom, a C1-C6 alkyl group, a C1-C6 alkoxy group, or C3-C6 A cycloalkyl group is represented and it is most preferable that it is a hydrogen atom.

R ³² and R ³³ may be the same as those of R ²¹ to R ²⁸ .

c represents the integer of 1-3 and it is most preferable that it is 1.

Among these, the phenolic hydroxyl group containing compound represented by following General formula (I) is especially preferable at the point which is excellent in high sensitivity and high residual film ratio.

[Formula 10]

(B) A component may be used individually by 1 type or may use 2 or more types together.

In the positive photoresist composition for liquid crystal device production of the present invention, when the component (B) is contained, the content ratio is preferably in the range of 1 to 25 parts by mass with respect to 100 parts by mass of the component (A), and is preferably 5 to 20 parts by mass. It is more preferable to exist in the range of a mass part. When the content ratio of the component (B) is 1 part by mass or more, the improvement effect of high sensitivity and high residual film ratio is improved. On the other hand, when it is 25 mass parts or less, generation | occurrence | production of the residue on the support body surface after alkali image development is suppressed. Moreover, since raw material cost is also suppressed, it is preferable.

<Other ingredients>

In the positive type photoresist composition for liquid crystal device production of the present invention, an additive having a miscible additive, for example, a photoresist composition, an adhesion improving agent, an antihalation agent, and a preservation agent for improving the adhesion between the layer and the lower layer thereof as desired. A stabilizer etc. can be added and contained suitably.

As a preferable adhesive agent, 2- (2-hydroxyethyl) pyridine is mentioned. By appropriately containing this in the positive photoresist composition for liquid crystal device production of the present invention, when forming a resist pattern on a metal film such as a Cr film, for example, adhesion between the layer made of the photoresist composition and the metal film can be effectively improved. Can be.

When it contains an adhesive improving agent, when the compounding quantity is too large, the change with time of the said photoresist composition will tend to deteriorate, and when too small, an adhesive improvement effect will not fully be acquired. Therefore, it is preferable to make content rate of an adhesive improver into the range of 0.1-10 mass parts with respect to the total solid of the positive photoresist composition for liquid crystal element manufacture.

As the antihalation agent, for example, an ultraviolet absorber for antihalation, specifically 2,2 ', 4,4'-tetrahydroxybenzophenone, 4-dimethylamino-2', 4'-dihydroxy Benzophenone, 5-amino-3-methyl-1-phenyl-4- (4-hydroxyphenylazo) pyrazole, 4-dimethylamino-4'-hydroxyazobenzene, 4-diethylamino-4'- Toxyazobenzene, 4-diethylamino azobenzene, curcumin, etc. can be contained suitably.

As explained above, the positive photoresist composition for liquid crystal element manufacture of this invention can improve the uniformity of the film thickness of a resist film.

In the LCD manufacturing field, a large substrate (for example, 360 mm x 460 mm or more) is usually used as compared with the silicon wafer used in the semiconductor device manufacturing field. In addition, the surface of the substrate to which the photoresist composition is applied differs in LCD production and semiconductor device production, such as very macro irregularities on the surface of the substrate for LCD manufacture and deformation of the substrate itself. Therefore, the photoresist composition for LCD manufacture and the photoresist composition for semiconductor element manufacture are technically different.

According to the positive type photoresist composition for liquid crystal element manufacture which concerns on this invention, it is excellent in the wettability with respect to a support body. This effect is effective even if the support on which the resist film is formed is a large glass rectangular substrate for LCD manufacture or a support on which a layer (surface layer) containing molybdenum as a main component such as a molybdenum layer or a molybdenum alloy layer is formed on the surface of the substrate. Obtained.

Therefore, in the present invention, such a positive photoresist composition can be suitably used for liquid crystal device production.

Moreover, the positive type photoresist composition for liquid crystal element manufacture of this invention spins by apply | coating the said photoresist composition to the whole application surface of a support body so that it may become finally required film thickness by the resist coating method by a discharge nozzle type. It can also be used suitably also for the method (spinless method) which does not. Moreover, after apply | coating the said photoresist composition to the whole coated surface of a support body, it can use suitably also for the method of adjusting a film thickness by spinning a support body.

In particular, in the latter method, generation of streaked traces after spin can be suppressed while suppressing the amount of resist coating. Therefore, the resist consumption can be reduced, the yield can be improved, and the cost can be reduced.

<Resist Pattern Forming Method>

The resist pattern formation method of this invention is a process of apply | coating the positive photoresist composition for liquid crystal element manufacture on the whole surface of the application | coating surface of a support body, the process of forming a resist film on the said support body, the process of exposing the said resist film, and the said resist film Alkali developing to form a resist pattern.

The resist pattern formation method of this invention can be performed as follows, for example.

First, the "coating process" which apply | coats the positive photoresist composition for liquid crystal element manufacture of this invention to the whole coating surface of a support body is performed.

It does not specifically limit as a support body, For example, the metal film which comprises a gate electrode is formed on insulated substrates, such as a glass substrate, and the said metal film becomes a surface layer, etc. 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, molybdenum tungsten or a molybdenum film.

As a support body, specifically, the laminated body in which the ITO wiring pattern of about 0.5 micrometer, the interlayer insulation layer pattern, and the molybdenum film were formed sequentially can be used, for example on a glass substrate.

The application of the positive photoresist composition for liquid crystal device manufacturing to the support may be performed by spin coating after central dropping (hereinafter, referred to as a central drop spin method) or by a resist nozzle coating method by a discharge nozzle type (hereinafter referred to as discharge nozzle type coating). It can be carried out by any method.

The center 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 a means for relatively moving the discharge nozzle and the support.

The discharge nozzle is not particularly limited as long as the photoresist composition discharged therefrom is configured to be applied in a band shape on the support, and for example, a discharge nozzle and a slit having a discharge port in which a plurality of nozzle holes are arranged in a column shape. A discharge nozzle having a discharge port in the shape can be used.

As this apparatus, TR63000S (product name; manufactured by Tokyo Oka Industries Co., Ltd.) of the coat & spinless system is known.

In addition, in a "coating process", after apply | coating the positive photoresist composition for liquid crystal element manufacture on a support body by a discharge nozzle type coating method etc., the means which spins a support body and adjusts a film thickness can also be used.

As a coating apparatus having this means, the SK-1100G (product name; Dainippon Screen Manufacturing Co., Ltd.) of the slit & spin method, CL1200 (product name; Tokyo Electron) of the scan coating + spin method by MMN (multi micro nozzle) And TR63000F (product name; manufactured by Tokyo Oka Industry Co., Ltd.) of the coat & spin method.

Especially in the field of LCD manufacture, it is preferable to make the film thickness of the resist film formed on a glass substrate into 0.5-2.5 micrometers, and it is more preferable to set it as 1.0-2.0 micrometers.

As a means for adjusting to the range of the said film thickness, after apply | coating the positive photoresist composition for liquid crystal element manufacture on a support body by the said discharge nozzle type coating method, it is preferable to use the method of spinning the said support body.

After applying the positive photoresist composition for liquid crystal device manufacturing to the whole surface of the support as described above, for example, the support on which the photoresist composition is applied is heated and dried (prebaked) at about 100 to 140 ° C. to form a resist film. Form. Thereafter, the resist film is subjected to selective exposure through a desired mask pattern.

The wavelength at the time of exposure can use ghi line (g line, h line, and i line) or i line preferably, and can implement it using each light source suitably.

Thereafter, the resist film after the selective exposure is developed using an alkaline developer consisting of an alkaline aqueous solution, for example, an aqueous solution of 1-10 mass% tetramethylammonium hydroxide (TMAH).

As a method of bringing an alkali developer into contact with a resist film, for example, a method of stacking a solution from one end of the support to the other end (a spin method), the support using an alkaline developer dropping nozzle provided at an upper portion near the center of the support It is possible to use a method of evenly contacting the alkaline developer to the entire surface.

And after leaving it for about 50 to 60 second for alkali image development, a resist pattern is obtained by performing the rinse process which wash | cleans the alkaline developer which remained on the resist pattern surface using rinse liquids, such as pure water.

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

Moreover, when the resist coating method by a discharge nozzle type is used, even if a support body size and apparatus size become large, a resist film can be formed on a support body without degrading application | coating uniformity and tact time.

In addition, when spin | coating after application | coating, since generation | occurrence | production of a stripe trace can be prevented, restraining application | coating amount of resist, it can contribute to reduction of manufacturing cost.

Example

Hereinafter, although the Example of this invention is described, the scope of the present invention is not limited to these Examples.

(Examples 1-9, Comparative Examples 1-2)

Each component shown in following Table 1 was mixed, and it melt | dissolved and prepared the positive type photoresist composition for liquid crystal element manufacture. Each symbol in Table 1 has the following meaning.

Alkali-soluble novolac resin (A)

As the component (A), a mixture of the following (A1) alone and three species (A1) to (A3) was used.

In Table 1, (5/2/3) which shows a mixing ratio in (A) component shows that (A1)-(A3) is a mixture mixed by mass ratio 5/2/3. The compounding quantity of (A) component in this photoresist composition was 100 mass parts.

(A1): Charge ratio (molar ratio) of m-cresol and p-cresol For the mixed phenols of this m-cresol / p-cresol = 60/40, formaldehyde is used as a condensing agent and a conventional method using an oxalic acid catalyst The novolak resin of Mw5000 obtained by fractionating the novolak resin obtained by condensation reaction with the water-methanol mixed solvent.

(A2): The novolak resin of Mw11000 obtained by the method similar to (A1).

(A3): Novolak of Mw6300 obtained by the same method as (A1) except that the mixing ratio (molar ratio) of m-cresol and p-cresol used the mixed phenols of m-cresol / p-cresol = 30/70. Suzy.

Naphthoquinone diazide group-containing compound (C)

The following (c1) was used as (C) component. The compounding quantity of (c1) in this photoresist composition was 23 mass parts with respect to a total of 100 mass parts of (A) component and (B) component.

(c1): The esterification reaction product of 1 mol of compounds represented by following General formula (II), and 2.34 mol of 1,2- naphthoquinone diazide-5-sulfonyl chlorides.

[Formula 11]

Organic solvents (D)

The following (d1) was used as (D) component. The compounding quantity of (d1) in this photoresist composition was 430 mass parts with respect to 100 mass parts of (A) component.

(d1): Propylene glycol monomethyl ether acetate (PGMEA).

Fluorine-based surfactants (E1)

The following (e11) and (e12) were used as (E1) component.

The compounding quantity of (e11) and (e12) in this photoresist composition shown in Table 1 is a value (unit: mass part) with respect to the total solid except the (D) component, (E1) component, and (E2) component.

(e11): A compound represented by the following general formula (E1-1-3) (trade name: Polyfox PF-656, manufactured by Ohmova Corporation).

[Formula 12]

(e12): A compound represented by the following general formula (E1-1-2) (trade name: Polyfox PF-6320, manufactured by Ohmova Corporation).

[Formula 13]

Polyester modified polydialkylsiloxane surfactant (E2)

The following (e2) was used as (E2) component.

The compounding quantity of (e2) in this photoresist composition shown in Table 1 is a value (unit: mass part) with respect to the total solid except the (D) component, (E1) component, and (E2) component.

(e2): BYK-310 (brand name, the product made by BIC Chemie).

Phenolic hydroxyl group-containing compound (B)

The following (b1) was used as (B) component. The compounding quantity of (b1) in this photoresist composition was 10 mass parts with respect to 100 mass parts of (A) component.

(b1): The compound (molecular weight 376) represented by following General formula (I).

[Formula 14]

Other ingredients

2- (2-hydroxyethyl) pyridine was used as another component. The compounding quantity of 2- (2-hydroxyethyl) pyridine in this photoresist composition was 0.25 mass parts with respect to the total solid of this photoresist composition.

(A) (mixing ratio) (Mw) (B) (C) (D) (E1) [Formulations] (E2) [Composition] Example 1 A1-(5000) b1 c1 d1 e11 [0.2] e2 [0.1] Example 2 A1 / A2 / A3 (5/2/3) (8000) Same as above Same as above Same as above Same as above Same as above Example 3 Same as above - Same as above Same as above Same as above Same as above Example 4 A1-(5000) b1 Same as above Same as above e12 [0.2] Same as above Example 5 A1 / A2 / A3 (5/2/3) (8000) - Same as above Same as above Same as above Same as above Example 6 A1-(5000) b1 Same as above Same as above e11 [0.2] - Example 7 Same as above Same as above Same as above Same as above e12 [0.2] - Example 8 Same as above Same as above Same as above Same as above e11 [0.1] e2 [0.1] Example 9 Same as above Same as above Same as above Same as above e12 [0.2] e2 [0.3] Comparative Example 1 Same as above Same as above Same as above Same as above - Same as above Comparative Example 2 Same as above Same as above Same as above Same as above - -

The positive photoresist composition for liquid crystal device production obtained above was filtered using a membrane filter having a pore diameter of 0.2 µm to form a "sample", and a resist film was formed by the method shown below using the said sample, and the edge bead Was evaluated, evaluation of streaked traces, and evaluation of uneven haze and dripping traces were performed, respectively.

<Formation of Resist Film>

The sample was applied onto a glass substrate (680 x 880 mm2) on which a molybdenum film was formed using a coating device (manufactured by Tokyo Oka Industries Co., Ltd., product name: TR-45) by a central dropping spin coating method, to obtain a predetermined thickness of 1.5 µm. A coating film was formed.

Subsequently, the temperature of the hot plate was 110 degreeC, and the 1st drying for 90 second was performed by the proximity baking which spaced about 1 mm. Subsequently, the temperature of the hot plate was 110 ° C, the glass substrate and the hot plate were bonded to each other, and the second drying was performed for 120 seconds to form a resist film having a thickness of 1.5 µm.

[Evaluation of Edge Bead]

The surface of the formed resist film was observed under a sodium lamp, and the edge bead width from the said edge part was calculated | required about the edge bead which generate | occur | produced at the edge part of the said glass substrate, and the edge bead was evaluated according to the following reference | standard. The results are shown in Table 2.

A: The edge bead width was 9 mm or less.

B: The edge bead width was more than 9 mm and 12 mm or less.

C: The edge bead width was more than 12 mm and less than 15 mm.

D: The edge bead width was 15 mm or more.

[Evaluation of Strip Shape Traces]

The surface of the formed resist film was observed under a sodium lamp, and the stripe traces were evaluated according to the following criteria. The results are shown in Table 2.

A: No occurrence of streaked traces was observed.

B: The generation | occurrence | production of the stripe shape trace was confirmed.

[Evaluation of Uneven Haze and Dropping Traces]

The surface of the formed resist film was observed under a sodium lamp, and evaluation of non-uniform haze and dripping traces was carried out according to the following criteria. The results are shown in Table 2.

A: The occurrence of nonuniform haze and dripping trace was not confirmed.

B: Although generation | occurrence | production of the nonuniform haze and the dripping trace was confirmed a little, it was the degree which was satisfactory practically.

C: The occurrence of nonuniform haze and dripping trace was confirmed.

Evaluation of the edge bead Assessment of Striped Geometry Traces Evaluation of Uneven Haze and Dropping Traces Example 1 A A A Example 2 A A A Example 3 A A A Example 4 B A A Example 5 B A A Example 6 A A B Example 7 A A B Example 8 A A A Example 9 B A B Comparative Example 1 D A A Comparative Example 2 - B -

As is clear from the results of Table 2, Examples 1 to 9 according to the present invention containing a fluorine-based surfactant (E1) have a better effect of reducing the edge bead width than those of Comparative Example 1, It was confirmed that uniformity was high. In particular, Examples 1-3 and 6-8 confirmed that the uniformity of the film thickness of a resist film was high.

In Examples 1 to 9, neither PFOAs nor PFOSs are used.

In addition, in Examples 1-9, the generation | occurrence | production of a stripe-shaped trace was not confirmed, and especially Examples 1-5, 8 are the same in that they are excellent in the conventional film | membrane property in that neither the generation | occurrence | production of a nonuniform haze and a dripping trace was confirmed at all. I could confirm that.

In the comparative example 2, since generation | occurrence | production of the stripe trace was confirmed, evaluation of an edge bit and uneven haze and dripping trace were not able to be performed.

Industrial availability

This invention is very useful industrially because it provides the positive type photoresist composition for liquid crystal element manufacture and the resist pattern formation method which can improve the uniformity of the film thickness of a resist film.

Claims (8)

Fluorine-type surfactant which has the alkylene oxide chain containing group represented by alkali-soluble novolak resin (A), a naphthoquinone diazide group containing compound (C), an organic solvent (D), and the following general formula (E1-0). (E1), The positive type photoresist composition for liquid crystal element manufacture characterized by the above-mentioned. [Formula 1]

[In formula (E1-0), R ^f is a fluorinated alkyl group having 1 to 6 carbon atoms, and R ¹¹ is an alkylene group or single bond having 1 to 5 carbon atoms.] The method of claim 1, The positive type photoresist composition for liquid crystal element manufacture which the said fluorine-type surfactant (E1) contains the compound which has a structure represented by the following general formula (E1-1). [Formula 2]

[In formula (E1-1), ^Rf is a C1-C6 fluorinated alkyl group; 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 1-50; n ² is 0 or 1] The method of claim 1, Furthermore, the positive type photoresist composition for liquid crystal element manufacture containing a silicone type surfactant (E2). The method of claim 3, wherein The positive type photoresist composition for liquid crystal element manufacture whose said silicone type surfactant (E2) is a polysiloxane type surfactant. The method of claim 4, wherein Polyester-modified polydialkylsiloxane surfactant (E2-1) in which the said 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). Positive photoresist composition for liquid crystal element manufacture containing. [Formula 3]

[In formula (E2-11), R <^1> is a C1-C3 linear or branched alkyl group, R <^2> is a C1-C15 linear or branched alkyl group. ; In formula (E2-12), R ¹ is the same as above, and R ³ is a polyester-modified group.] The method of claim 3, wherein For producing a liquid crystal device in which the mixing ratio [(E1) / (E2)] of the fluorine-based surfactant (E1) and the silicon-based surfactant (E2) is (E1) / (E2) = 1/9 to 9/1 by mass ratio Positive photoresist composition. The method of claim 1, Furthermore, the positive type photoresist composition for liquid crystal element manufacture containing the phenolic hydroxyl group containing compound (B) of molecular weight 1000 or less. Applying the positive type photoresist composition for liquid crystal device production according to claim 1 to the entire application surface of the support by moving the discharge nozzle and the support relatively, forming a resist film on the support, exposing the resist film, And alkali developing the resist film to form a resist pattern.