KR20150053712A - Positive resist composition, method of forming resist pattern, method of forming pattern comprising metal layer, and method of producing through electrode - Google Patents

Abstract

In the present invention, provided is a positive type resist composition, which is allowed to hardly generate faults in a shape caused by a post-bake, comprising (A) an alkali-soluble resin which has a novolak resin with (a1) p-cresol repeating unit and (a2) m-cresol repeating unit as main ingredients; (B) a phenol compound; and (C) photosensitive components wherein the novolak resin comprises (A1) a novolak resin whose a mixing mole ratio of (a1) the repeating unit and (a2) the repeating unit is between 6 to 4 and 9 to 1; and (A2) a novolak resin whose a mixing mole ratio of (a1) the repeating unit and (a2) the repeating unit is between 1 to 9 and 4 to 6.

Description

TECHNICAL FIELD [0001] The present invention relates to a positive resist composition, a resist pattern forming method, a method of forming a pattern comprising a metal layer, and a manufacturing method of a through electrode. }

The present invention relates to a positive resist composition and a resist pattern forming method, a method of forming a pattern made of a metal layer, and a method of manufacturing a through electrode.

BACKGROUND ART [0002] In general, a photolithography technique is used for manufacturing a liquid crystal display element used in a flat panel display (FPD) such as a liquid crystal display or a plasma display. For example, a resist composition is applied onto a conductive thin film for electrodes such as a metal layer formed on one surface of a substrate to form a resist film, exposed and developed, post-baked to form a resist pattern, By etching the metal layer using the mask, a desired pattern of the metal layer is formed on the substrate to produce an electrode.

In the production of a liquid crystal display element in FPD, a large substrate is used unlike the case of semiconductor device manufacturing. Therefore, the resist materials used for the production of liquid crystal display devices are focused on improvement of macroscopic characteristics (coating properties, non-uniform heating, non-uniformity of development, etc.) rather than microscopic characteristics required especially in the case of semiconductor device production.

For example, a positive resist composition comprising an alkaline-soluble novolak resin and a naphthoquinone diazide group-containing compound dissolved in an organic solvent containing a specific diol has been proposed for the purpose of improving coatability on a large- (See, for example, Patent Document 1).

Japanese Laid-Open Patent Publication No. 2012-177774

In recent years, in the production of a liquid crystal display element in an FPD, post-baking is performed at a high temperature (for example, 130 DEG C or more) in order to improve the adhesion between the substrate having the metal layer and the insulating layer and the resist pattern, .

In addition, by post-baking at a high temperature, the resist pattern can be flowed into a tapered shape. In the manufacture of a liquid crystal display element in an FPD, metal wiring is formed on a tapered resist pattern formed by the above flow by a technique such as chemical vapor deposition (CVD). At this time, in order to avoid problems such as disconnection of the metal wiring, it is necessary to precisely control the flow shape of the resist pattern.

However, in a conventional resist composition, a step (rabbit) is formed on the surface of the resist pattern by the post-baking at a high temperature, and the defect shape of the resist pattern tends to occur. When the dry etching process is performed on the resist pattern having the step (rabbit ears), a part of the step is peeled off from the resist pattern to become a foreign matter, which causes a problem of disconnection.

SUMMARY OF THE INVENTION 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 resist composition which does not cause defective shape due to post-baking.

In order to solve the above problems, the present invention employs the following configuration.

That is, the first embodiment of the present invention is a method for producing a phenol compound (B) comprising an alkali-soluble resin component (A) containing a novolac resin having as a main component a p-cresol repeating unit (a1) and an m- ) And a photosensitive component (C), wherein the novolak resin is a positive resist composition wherein the mixing ratio (molar ratio) of the repeating unit (a1) to the repeating unit (a2) A novolak resin (A1) having a unit (a2) = 6/4 to 9/1 and a novolak resin (A2) having a repeating unit (a1) / a repeating unit (a2) = 1/9 to 4/6 Wherein the resist composition is a positive resist composition.

A second aspect of the present invention is a method for producing a resist pattern, comprising the steps of: (1) forming a resist film on a support using the positive resist composition of the first aspect of the present invention; (2) exposing the resist film; A step (3) of forming a pre-pattern by development and a step (4) of forming a resist pattern by heating the pre-pattern.

In a third aspect of the present invention, there is provided a method of forming a resist pattern, comprising the steps of: forming a resist pattern on the metal layer by a resist pattern forming method according to the second aspect of the present invention, A step of obtaining a laminate, and a step of forming a pattern of the metal layer by performing a dry etching treatment on the laminate.

A fourth aspect of the present invention is a manufacturing method of a penetrating electrode characterized by using a method of forming a pattern made of a metal layer according to the third aspect of the present invention.

According to the present invention, it is possible to provide a positive resist composition that does not cause defective shape due to post-baking.

Fig. 1 is a schematic diagram showing a typical shape model of a post-baked resist pattern corresponding to evaluation (⊚, ◯, ×) of the resist pattern shape in [Example].

In the present specification and claims, "alkyl group", unless otherwise specified, includes linear, branched, and cyclic monovalent saturated hydrocarbon groups.

"Repeating unit" means a monomer unit (monomer unit) constituting a polymer compound (resin, polymer, copolymer). The p-cresol repeating unit is represented by a structure derived from p-cresol alone and does not include a structure derived from a condensing agent. The same shall apply to the m-cresol repeating unit.

The term " styrene " includes the concept that hydrogen atoms at the [alpha] -position of styrene and styrene are substituted with other substituents such as an alkyl group and a halogenated alkyl group.

The term " hydroxystyrene " includes the concept that the hydrogen atom at the [alpha] -position is substituted with another substituent such as an alkyl group or a halogenated alkyl group.

&Quot; Exposure " is a concept including the entire irradiation of radiation.

≪ Positive Resist Composition >

The positive resist composition of the present invention is a positive resist composition comprising an alkali-soluble resin component (A) (hereinafter referred to as "component (A)") containing a novolac resin having as a main component a p- ), A phenol compound component (B) (hereinafter also referred to as "component (B)"), and a photosensitive component (C) (hereinafter also referred to as "component (C)").

≪ Alkali-soluble resin component (A) >

In the positive resist composition of this embodiment, the component (A) contains a novolak resin containing as a main component a p-cresol repeating unit (a1) and an m-cresol repeating unit (a2).

The content of the novolak resin containing as a main component the p-cresol repeating unit (a1) and the m-cresol repeating unit (a2) in the component (A) is preferably 80% by mass or more, more preferably 90% , More preferably 95 mass% or more, and 100 mass%, and most preferably 100 mass%. If the content of the novolak resin in the component (A) is not lower than the lower limit, the post-baking defects are not generated more easily in forming the resist pattern.

The "novolak resin containing, as a main component, the p-cresol repeating unit (a1) and the m-cresol repeating unit (a2)" as used herein means a repeating unit derived from all the repeating units derived from phenols constituting the novolak resin, Means a novolak resin having a total content of the repeating unit (a1) and the m-cresol repeating unit (a2) of not less than 50 mol%, preferably not less than 80 mol% The novolak resin having a total of 100 mole% of the cresol repeating units (a2) may be used.

The novolac resin containing the p-cresol repeating unit (a1) and the m-cresol repeating unit (a2) as a main component is a novolac resin (hereinafter also referred to as "component (A1)") (A2) (hereinafter also referred to as " component (A2) ").

[Novolak resin (A1)]

(A1) / repeating unit (a2) = 6/4 to 9/1, wherein the mixing ratio (molar ratio) of the p-cresol repeating unit (a1) to the m- Novolak resin.

(A1) / repeating unit (a2) = 6/4 to 8/2, and more preferably 6/4 to 7/3 (molar ratio) in the component (A1) to be. When the mixing ratio in the component (A1) is within the above range, the shape of the pre-pattern becomes good. In addition, the film thickness of the resist film before development can be easily maintained even after development / post-baking (the residual film property is improved).

The mixing ratio (molar ratio) of the component (A1) to the component (A1) is such that the mixing ratio (molar ratio) of the p-cresol repeating unit (a1) to the m- .

The component (A1) may have other repeating units in addition to the p-cresol repeating unit (a1) and the m-cresol repeating unit (a2).

The content ratio of the total of the p-cresol repeating unit (a1) and the m-cresol repeating unit (a2) in the entire repeating units derived from the phenol constituting the component (A1) is preferably at least 50 mol% , Preferably 80 to 100 mol%, and particularly preferably 100 mol%.

When the component (A1) has other repeating units, one or more other repeating units in the component (A1) may be used.

Examples of other repeating units include repeating units derived from p-cresol and phenols other than m-cresol.

Phenols other than p-cresol and m-cresol include, for example, phenol, o-cresol; Xylylenols such as 2,3-xylenol, 2,5-xylenol, 3,5-xylenol and 3,4-xylenol; tert-butylphenol, 3-tert-butylphenol, 2-tert-butylphenol, 2-ethylphenol, alkyl phenols such as tert-butyl phenol, 2-tert-butyl-4-methyl phenol and 2-tert-butyl-5-methyl phenol; alkoxyphenols 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; 4,4'-dihydroxybiphenyl, bisphenol A, resorcinol, hydroquinone, pyrogallol, and the like.

The mass average molecular weight (Mw) of the component (A1) is preferably 2000 to 8000, more preferably 3000 to 7000, and still more preferably 3500 to 6500.

When the Mw of the component (A1) is within the above range, the shape and residual film properties of the pre-pattern become better.

In the present invention, the "weight average molecular weight (Mw)" is defined as the weight average molecular weight in terms of polystyrene calculated by gel permeation chromatography (GPC).

[Novolak resin (A2)]

(A2) is a mixture in which the mixing ratio (molar ratio) of the p-cresol repeating unit (a1) and the m-cresol repeating unit (a2) is in the range of the repeating unit (a1) / repeating unit (a2) = 1/9 to 4/6 It is a volak resin.

(A1) / repeating unit (a2) = 2/8 to 4/6, and more preferably 3/7 to 4/6 (molar ratio) in the component (A2) to be. When the mixing ratio in the component (A2) is within the above range, the flow property at the time of post-baking can be improved.

The mixing ratio (molar ratio) of the component (A2) to the component (A2) is such that the mixing ratio (molar ratio) of the p-cresol repeating unit (a1) to the m- .

(A2) may have other repeating units in addition to the p-cresol repeating unit (a1) and the m-cresol repeating unit (a2).

The content ratio of the total of the p-cresol repeating unit (a1) and the m-cresol repeating unit (a2) in the entire repeating units derived from the phenol constituting the component (A2) is preferably 50 mol% , More preferably 80 to 100 mol%, and particularly preferably 100 mol%.

When the component (A2) has other repeating units, the number of the other repeating units in the component (A2) may be one or two or more.

Examples of other repeating units include repeating units derived from the above-mentioned phenols other than p-cresol and m-cresol.

(A2) is preferably a group represented by the following formula (x1) (hereinafter referred to as a group (x1)) in addition to the p-cresol repeating unit (a1) and the m- ) And a group represented by the following formula (x2) (hereinafter also referred to as " group (x2) ").

Since the group (x1) and the group (x2) are contained, a tapered resist pattern which does not cause a shape abnormality is easily obtained at the time of flow by the post-baking.

[Chemical Formula 1]

[In the formula, * indicates a binding hand.]

The mixing ratio of the group (x1) and the group (x2) in the component (A2) can be selected, for example, by selecting the type of aldehyde (formaldehyde, salicylaldehyde) as a condensing agent when synthesizing the component (A2) And is set by adjusting the injection amount. (X1) is introduced into the component (A2) by selecting formaldehyde as a condensing agent, and the group (x2) is introduced by selecting salicylaldehyde.

(X1) / group (x2) = 30/1 to 5/1, and more preferably 15/1 to 5/1 as the mixing ratio (molar ratio) of the group (x1) and the group (x2) in the component (A2) 1 to 8/1. This mixing ratio (molar ratio) is determined by the amount of formaldehyde and salicylaldehyde introduced.

The content ratio of the group (x2) in the component (A2) is determined, for example, by the ratio of the amount of the salicylaldehyde to the total amount of the cresol to be used for synthesizing the component (A2). The ratio of the amount of salicylaldehyde to be injected is preferably 1% by mass or more, more preferably 3 to 20% by mass, and still more preferably 5 to 15% by mass with respect to the total amount of cresol introduced.

When the content ratio of the group (x2) is not lower than the preferable lower limit value, the heat resistance of the resist pattern is further improved. In addition, it is easy to obtain a good taper shape (a shape that does not generate a shape abnormality (rabbit ears) at the time of flow). On the other hand, when the content ratio of the group (x2) is not more than the preferable upper limit value, the lowering of the flow property during post-baking is suppressed and the residual film property is easily maintained.

The weight average molecular weight (Mw) of the component (A2) is preferably from 2,000 to 30,000, more preferably from 5,000 to 25,000, and still more preferably from 8,000 to 20,000.

When the Mw of the component (A2) is within the above range, the flow property at the time of post-baking can be improved.

(Mass ratio) of the component (A1) to the component (A2) is preferably 5/5 to 9/1, more preferably 5/5 To 8/2, and more preferably from 6/4 to 7/3.

If the mixing ratio (mass ratio) of the component (A1) and the component (A2) is greater than or equal to the preferable lower limit value, the residual film property tends to be maintained. On the other hand, Lt; / RTI >

The novolac resin containing as a main component the p-cresol repeating unit (a1) and the m-cresol repeating unit (a2) may contain novolac resins other than the novolak resin (A1) and the novolak resin (A2) do.

the total content of the novolak resin (A1) and the novolak resin (A2) in the novolak resin containing as a main component the p-cresol repeating unit (a1) and the m-cresol repeating unit (a2) is 80 mass% , More preferably 90 mass% or more, and 100 mass%, and most preferably 100 mass%. When the total content of the component (A1) and the component (A2) in the novolac resin is more than or equal to the preferable lower limit value, defects in shape due to post-baking do not occur more easily in the formation of the resist pattern.

In the positive resist composition of the present embodiment, the total content of the novolak resin (A1) and the novolak resin (A2) in the component (A) is preferably 70% by mass or more, more preferably 80% , More preferably 90 mass% or more, and 100 mass%, and most preferably 100 mass%. If the total content of the component (A1) and the component (A2) is lower than the lower limit, the post-baking defects do not occur more easily in forming the resist pattern.

The novolac resin containing, as a main component, a p-cresol repeating unit (a1) and an m-cresol repeating unit (a2) is, for example, obtained by reacting p-cresol, m-cresol and aldehydes under an acidic catalyst have. In this reaction, novolac resin (A1) and novolak resin (A1) having the repeating unit (a1) and the repeating unit (a2) thereof at a predetermined mixing ratio are obtained by controlling the injection ratio of p- A2), respectively.

The reaction of p-cresol, m-cresol and aldehydes can be carried out in a known manner under an acidic catalyst. As the acid catalyst, hydrochloric acid, sulfuric acid, formic acid, oxalic acid, paratoluenesulfonic acid and the like can be used.

Examples of the aldehydes include formaldehyde, paraformaldehyde, trioxane, acetaldehyde, propionaldehyde, butylaldehyde, trimethylacetaldehyde, acrolein, crotonaldehyde, cyclohexanaldehyde, furfural, furyl acrolein, benzaldehyde, terephthalaldehyde, phenyl O-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, o-hydroxybenzaldehyde, Chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, cinnamaldehyde, and salicylaldehyde. These may be used alone, or two or more of them may be used in combination.

For the novolak resin (A2), when reacting p-cresol, m-cresol and aldehydes, salicylaldehyde is preferably used as the aldehyde. For example, formaldehyde and salicylaldehyde are used as aldehydes, preferably in the range of formaldehyde: salicylaldehyde (molar ratio) = 30: 1 to 5: 1, more preferably 15: 1 to 8 : 1, and is a novolac resin obtained by reacting with p-cresol and m-cresol. By using this novolak resin in combination with the component (A1), the pattern shape before post-baking can be made good (shape in which the shape abnormality (rabbit) is not generated well during flow).

When salicylaldehyde is used as the condensing agent in the production of the novolak resin (A2), the heat resistance of the resin is also higher than that in the case of using formaldehyde.

The positive resist composition of the present embodiment may be used as the component (A) in combination with an alkali-soluble resin not corresponding to the novolac resin described above.

The alkali-soluble resin not corresponding to the above-mentioned novolak resin is not particularly limited and may be arbitrarily selected from those which can be usually used as a film-forming material in a positive resist composition. Examples thereof include phenol resins, acrylic resins, copolymers of styrene and acrylic acid, polymers of hydroxystyrene, polyvinylphenol, poly-a-methylvinyl phenol, and the like known as base components of positive resist compositions.

The Mw of the whole component (A) is preferably from 2,000 to 50,000, more preferably from 2,000 to 40,000, and still more preferably from 2,000 to 30,000.

Among them, the component (A) preferably contains the component (A1) having a mass average molecular weight of 2000 to 8000 and the component (A2) having a mass average molecular weight of 2000 to 30,000.

In the positive resist composition of this embodiment, the content of the component (A) may be adjusted depending on the thickness of the resist film to be formed.

≪ Phenol compound component (B) >

In the positive resist composition of the present embodiment, a compound containing a phenolic hydroxyl group (phenolic hydroxyl group-containing compound) is used for the component (B) from the viewpoint of improving the sensitivity and the like.

Particularly, in the field of FPD manufacturing, improvement in throughput is a very large problem. However, by using the component (B), high sensitivity is achieved and contributes to improvement in throughput. Further, by using the component (B), since the surface-hardened layer is strongly formed on the resist film, the amount of decrease in the film thickness of the resist film of the unexposed portion at the time of development is small and occurrence of development unevenness caused by the difference in development time is suppressed do.

As the component (B), it is preferable to use a phenolic hydroxyl group-containing compound having a low molecular weight since an effect of improving the sensitivity is easily obtained. The molecular weight of the component (B) is preferably 1,000 or less, and more preferably 200 to 1,000.

Specific examples of the component (B) include a compound represented by the following general formula (b1) (hereinafter also referred to as "component (b1)").

(2)

Wherein R ¹ and R ² are each independently a hydroxyl group or an alkyl group having 1 to 5 carbon atoms, and n 1 and n 2 are each independently an integer of 0 to 3.]

In the formula (b1), R ¹ and R ² are each independently a hydroxyl group or an alkyl group having 1 to 5 carbon atoms. The alkyl group having 1 to 5 carbon atoms in R ¹ and R ² is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, more preferably a linear alkyl group having 1 to 5 carbon atoms. Specific examples include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl and neopentyl.

In the formula (b1), n1 and n2 each independently represent an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 1. n1 and n2 may be the same or different from each other and are preferably the same as each other.

When n1 and n2 are both an integer of 1 to 3, R ¹ and R ² may be the same as or different from each other, and are preferably the same as each other. The bonding position of the two is not particularly limited, but is preferably bonded at a position symmetrical to the left in the component (b1).

When n1 is 2 or 3, plural R ^{1 s} may be the same as or different from each other, and when n2 is 2 or 3, plural R ^{2 s} may be the same or different.

In the formula (b1), each of the necessary hydroxyl groups bonded to the phenyl group is not particularly limited, but is preferably bonded at a position symmetrical in the component (b1).

Specific examples of the component (b1) are listed below.

(3)

Specific examples of the component (B) include a phenol compound represented by the following general formula (b2) (hereinafter also referred to as "component (b2)").

[Chemical Formula 4]

Wherein R ¹¹ to R ¹⁸ 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 a cycloalkyl group having 3 to 6 carbon atoms. R ¹⁹ to R ²¹ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; Of Q is a group (formula (b2-r) is combined with a hydrogen atom, an alkyl group, R ¹⁹ having 1 to 6 carbon atoms represented by the group, or the formula (b2-r) to form a cycloalkyl group having a carbon number of 3 ~ 6, R ²² And R ²³ 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 a cycloalkyl group having 3 to 6 carbon atoms, and c represents an integer of 1 to 3. . a and b each independently represent an integer of 1 to 3, d represents an integer of 0 to 3, and n represents an integer of 0 to 3.]

In formula (b2), R ¹¹ to R ¹⁸ 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 a cycloalkyl group having 3 to 6 carbon atoms.

Examples of the halogen atom represented by R ¹¹ to R ¹⁸ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferable.

The alkyl group having 1 to 6 carbon atoms is preferably a linear or branched alkyl group having 1 to 6 carbon atoms. Specific examples thereof include a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, and a hexyl group.

As the alkoxy group having 1 to 6 carbon atoms, a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, a n-butoxy group and a tert-butoxy group are preferable, and a methoxy group and an ethoxy group are more preferable.

Examples of the cycloalkyl group having 3 to 6 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

Among them, each of R ¹¹ to R ¹⁸ is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom or a linear alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom or a methyl group And particularly preferably a hydrogen atom.

In the formula (b2), R ¹⁹ to R ²¹ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. The description of the alkyl group having 1 to 6 carbon atoms in R ¹⁹ to R ²¹ is the same as the alkyl group having 1 to 6 carbon atoms in R ¹¹ to R ¹⁸ .

Among them, R ¹⁹ to R ²¹ each independently represent a hydrogen atom or a linear alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.

In the formula (b2), Q represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a group bonded to R ¹⁹ to form a cycloalkyl group having 3 to 6 carbon atoms, or a group represented by the formula (b2-r). The description of the alkyl group having 1 to 6 carbon atoms in Q is the same as the alkyl group having 1 to 6 carbon atoms in R ¹¹ to R ¹⁸ . The description of the cycloalkyl group having 3 to 6 carbon atoms formed by combining with R ^{19 in} Q is the same as the cycloalkyl group having 3 to 6 carbon atoms in R ¹¹ to R ¹⁸ .

When Q is a group represented by the following general formula (b2-r), formula (b2-r) of the R ²² and R ²³ are, 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 a cycloalkyl group having 3 to 6 carbon atoms; and c represents an integer of 1 to 3. R ²² and description of a halogen atom, an alkoxy group, or a cycloalkyl group having 3 to 6 carbon atoms of 1 to 6 carbon atoms alkyl group, having 1 to 6 in the R ²³ is a halogen atom in the above-mentioned R ¹¹ ~ R ¹⁸ , An alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 6 carbon atoms.

Among them, Q is formula (b2-r) according to that formula (b2-r), and preferably a group represented by, R ²² and R ²³ are each independently preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms ( A straight chain alkyl group having 1 to 6 carbon atoms, more preferably a methyl group), and c is preferably 1 or 2.

In formula (b2), a and b each independently represent an integer of 1 to 3, d represents an integer of 0 to 3, and n represents an integer of 0 to 3.

 Specific examples of the compound (b2) represented by the general formula (b2) include tris (4-hydroxyphenyl) methane, bis (4-hydroxy- (4-hydroxy-2,3,5-trimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy- 3-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy- Dimethylphenyl) -4-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -3- hydroxyphenylmethane, bis Hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -3,4-dihydroxyphenylmethane, bis Hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -2,4-dihydroxyphenylmethane, bis Hydroxyphenyl) -3-methoxy-4-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy- (5-cyclohexyl-4-hydroxyphenyl) -2-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy Methylphenyl) -3,4-dihydroxyphenylmethane, bis (2,3,5-trimethyl-4-hydroxyphenyl) -2- hydroxyphenylmethane, 1- [1- Phenyl] isopropyl] -4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene, 1- [ (2 ', 3', 4'-trihydroxyphenyl) ethyl] benzene, 2- (2,3,4-trihydroxyphenyl) -2- Propane, 2- (2, 4'-dihydroxyphenyl) -2- (4'-hydroxyphenyl) ) Propane, 2- (3-fluoro-4-hydroxyphe 2- (4'-hydroxyphenyl) propane, 2- (3'-fluoro-4'- Hydroxyphenyl) -2- (4'-hydroxyphenyl) propane, 2- (2,3,4-trihydroxyphenyl) -2- Bis (2,4-dihydroxyphenyl) methane, 2,3,4-trihydroxyphenyl-4'- Hydroxyphenylmethane, 1,1-di (4-hydroxyphenyl) cyclohexane, and 2,4-bis [1- (4-hydroxyphenyl) isopropyl] -5-hydroxyphenol.

Among these, bis (4-hydroxy-3-methylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-2,3,5-trimethylphenyl) (2,3,5-trimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane, 2,4-bis [1- (4-hydroxyphenyl) isopropyl] -5 Dihydroxyphenyl) cyclohexane, 1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4-hydroxyphenyl) (4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene is preferable since it is excellent in the high sensitivity, the Gojan film thickness and the linearity improvement effect. -Hydroxyphenyl) ethyl] benzene, and bis (2,3,5-trimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane.

As the component (B), one kind may be used alone, or two or more kinds may be used in combination.

Among the above, in the positive resist composition of the present embodiment, it is preferable to use the component (b1) as the component (B), in addition to the high sensitivity,

In the positive resist composition of the present embodiment, by using the component (A2) together with the component (A1), a step (rabbit) is not formed well on the surface of the resist pattern even when post- A resist pattern of a good shape can be obtained. However, the component (A2) has a lower dissolution inhibiting effect at the time of development than the component (A1). On the other hand, by using the component (b1) as the component (B), the sensitivity can be increased and the molecular weight of the component (A) can be easily increased. Thereby, the dissolution-inhibiting effect of the resist film is improved, and the residual film property of the resist film is enhanced.

The content of the component (B) in the positive resist composition of the present embodiment is preferably 3 to 25 parts by mass, more preferably 3 to 20 parts by mass, still more preferably 5 to 20 parts by mass, per 100 parts by mass of the component (A) 15 parts by mass.

On the other hand, if the content of the component (B) is not more than the preferable upper limit value, residues are easily generated on the surface of the substrate after the development, and if the content of the component (B) is lower than the preferable lower limit value, And the raw material cost is also suppressed.

≪ Photosensitive component (C) >

In the positive resist composition of the present embodiment, the component (C) is not particularly limited, and a photosensitive component mixed with a resist material for producing a liquid crystal display element or the like can be used.

Examples of the component (C) include an esterification reaction product (c1) of a phenolic hydroxyl group-containing compound and a 1,2-naphthoquinone diazidesulfonic acid compound represented by the following formula (c1-0) ) Component ") is preferable.

[Chemical Formula 5]

Examples of the 1,2-naphthoquinone diazidesulfonic acid compound include 1,2-naphthoquinonediazide-5-sulfonyl compounds, 1,2-naphthoquinonediazide-4-sulfonyl compounds and the like , 1,2-naphthoquinonediazide-5-sulfonyl compound are preferable.

Preferable specific examples of the component (c1) are shown below.

[Chemical Formula 6]

In formula (c1-1), D ¹ to D ⁴ each independently represent a hydrogen atom or a 1,2-naphthoquinonediazide-5-sulfonyl group, at least one of D ¹ to D ⁴ represents 1, 2-naphthoquinonediazide-5-sulfonyl group.

The esterification rate of the component (c1) is preferably 50 to 70%, more preferably 55 to 65%. When the esterification ratio is 50% or more, the film reduction after alkali development is further suppressed, and the residual film ratio is increased. When the esterification ratio is 70% or less, the storage stability is further improved.

The term "esterification ratio" as used herein means, for example, that the compound represented by the formula (c1-1) is a compound wherein D ¹ to D ⁴ in the formula (c1-1) are 1,2- - represents a substitution by a sulfonyl group.

The component (c1) is also preferable from the viewpoint of preparing a positive resist composition which is very inexpensive and highly sensitive.

As the component (C), other quinonediazide esters (c2) (hereinafter also referred to as "component (c2)") other than the component (c1) may be used.

Examples of the component (c2) include a phenol compound (component (b2)) represented by the aforementioned general formula (b2) and a 1,2-naphthoquinone diazidesulfonic acid compound (preferably a 1,2- Quinonediazide-5-sulfonyl compound or 1,2-naphthoquinonediazide-4-sulfonyl compound).

As the component (C), one kind may be used alone, or two or more kinds may be used in combination.

In the positive resist composition of this embodiment, it is preferable to use the component (c1) as the component (C) among the above.

The content of the component (C) in the positive resist composition of the present embodiment is preferably 15 to 40 parts by mass, more preferably 20 to 35 parts by mass with respect to 100 parts by mass of the total of the components (A) and (B) More preferably 20 to 30 parts by mass.

When the content of the component (C) is lower than the preferable lower limit value, a resist pattern having a good shape is easily formed. On the other hand, if the content of the component (B) is not more than the preferable upper limit value, the sensitivity and resolution are improved, and the generation of the residue after the alkali developing treatment is suppressed.

<Other ingredients>

(A), (B) and (C) are dissolved in an organic solvent component (S) (hereinafter, also referred to as "component (S)") in the positive resist composition of this embodiment And then dissolved.

[Organic solvent component (S)]

Examples of the component (S) include lactones such as? -Butyrolactone; Ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone and 2-heptanone; Polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, hexylene glycol and dipropylene glycol; A compound having an ester bond such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate; a monomethyl ether, monoethyl ether, Monoalkyl ethers such as monopropyl ether and monobutyl ether, and compounds having an ether bond such as monophenyl ether [among these, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME) is preferred; Cyclic ethers such as dioxane; And esters such as ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate and ethyl ethoxypropionate.

As the component (S), one type may be used alone, or two or more types may be used in combination.

Among these, propylene glycol monomethyl ether acetate (PGMEA) is preferable because it imparts excellent coating properties and the resist film on a large glass substrate gives excellent film thickness uniformity.

As the component (S), it is also preferable to use an organic solvent other than PGMEA and PGMEA. Examples of such an organic solvent include ethyl lactate,? -Butyrolactone, propylene glycol monobutyl ether, and hexylene glycol. Ethyl lactate,? -Butyrolactone, and hexylene glycol are preferable, Silylene glycol is particularly preferred.

When PGMEA and hexylene glycol are used in combination, hexylene glycol is preferably compounded in a mass ratio, preferably 0.01 to 0.05 times, more preferably 0.015 to 0.03 times, based on PGMEA.

When PGMEA and ethyl lactate are used in combination, ethyl lactate is compounded in a mass ratio, preferably 0.1 to 10 times, more preferably 1 to 5 times, to PGMEA.

When PGMEA and? -Butyrolactone are used in combination,? -Butyrolactone is compounded in a mass ratio, preferably 0.01 to 1 time, more preferably 0.05 to 0.5 time, relative to PGMEA.

In the positive resist composition of the present embodiment, the amount of the component (S) to be used is not particularly limited and is appropriately set in accordance with the thickness of the coating film and the coating property at a concentration that can be applied to a substrate or the like. (S) such that the total amount of the components (A) to (C) in the positive resist composition is in the range of 30 mass% or less, more preferably 20 to 28 mass% Ingredients are used.

In addition to the components (A) to (C) and the component (S), the positive resist composition of this embodiment may contain an ultraviolet absorber for preventing halation, for example, 2,2 ' 4-dihydroxybenzophenone, 5-amino-3-methyl-1-phenyl-4- (4-hydroxyphenyl azo) Pyrazole, 4-dimethylamino-4'-hydroxyazobenzene, 4-diethylamino-4'-ethoxyazobenzene, 4-diethylaminoazobenzene, curcumin and the like; Fluorinated surfactants such as fluororads FC-430 and FC431 (trade name, manufactured by Sumitomo 3M Co., Ltd.), F-top EF122A, EF122B, EF122C and EF126 (trade name, manufactured by Tohchem Products Co., Ltd.); Storage stabilizers such as benzoquinone, naphthoquinone, and p-toluenesulfonic acid; If necessary, additives such as an additive resin, a plasticizer, a stabilizer, and a contrast improver may be added and contained.

In the positive resist composition of the present embodiment, the positive resist composition contains the alkali-soluble resin component (A), the phenol compound component (B) and the photosensitive component (C) A novolak resin (A2) having a high ratio of the novolak resin (A1) having a high ratio to the m-cresol repeating unit (a2) is used in combination.

In a positive resist composition containing only a novolak resin having a high proportion of the p-cresol repeating unit (a1) as the component (A), the pre-pattern obtained by the resist pattern formation has an excessively high square- (Rabbit) is easily formed on the surface of the resist pattern by the post-baking. When this step (rabbit ears) is formed, there is a problem that a part of the stepped portion is peeled off from the resist pattern to become a foreign material when dry etching is performed, thereby causing disconnection.

In the positive resist composition of this embodiment, the action of the combination of the novolak resin (A2) having a high proportion of the (A1) component having a high proportion of the p-cresol repeating unit (a1) and the m-cresol repeating unit (a2) A pre-pattern having a tapered shape that does not generate a shape abnormality well and a good flow property is formed in advance. Therefore, the step (rabbit) is not formed well in the resist pattern formation. Further, since the shape defect due to the post-baking is hardly generated, the occurrence of disconnection is also suppressed.

The positive resist composition of this embodiment is particularly preferable as a resist composition used in the production of a flat panel display (FPD), which includes a process in which the post-baking is performed at a high temperature (for example, 130 占 폚 or more).

&Lt; Method of forming resist pattern &

The resist pattern forming method of the present invention comprises the steps of (1) forming a resist film on a support using the above-mentioned positive resist composition of the present invention, (2) exposing the resist film, A step (3) of forming a pre-pattern, and a step (4) of forming a resist pattern by heating the pre-pattern.

The resist pattern forming method of this embodiment can be carried out, for example, as follows.

Step (1) of forming a resist film:

First, the positive resist composition of the present embodiment is coated on a support with a spinner or the like and baked (post-apply baking (PAB)) treatment is performed for 40 to 120 seconds at a temperature of, for example, Preferably 60 to 90 seconds, to form a resist film.

At this time, the thickness of the resist film is preferably about 0.5 to 2.5 占 퐉, more preferably about 1.0 to 2.0 占 퐉, for example, in the case of FPD production.

Step (2) of exposing the resist film:

Next, the resist film is subjected to selective exposure through a mask (mask pattern) having a predetermined pattern formed thereon by using a light source that emits ultraviolet light, for example, a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, or a xenon lamp.

A step (3) of developing a resist film after exposure to form a pre-pattern;

Next, the exposed resist film is developed. The developing treatment is carried out by, for example, liquid mounting an alkaline aqueous solution such as an aqueous 1 to 10 mass% tetramethylammonium hydroxide (TMAH) solution from one end of the support to the other end, And spreading the coating liquid over the entire surface of the support from the developing liquid dropping nozzle.

Then, it is stopped for about 50 to 90 seconds and developed to form a free pattern on the support.

After the developing treatment, rinsing treatment is preferably carried out. The rinse treatment is carried out, for example, by cleaning the developer remaining on the surface of the pre-pattern using a rinsing liquid such as pure water.

Step (4) of forming a resist pattern by heating the pre-pattern:

After the development treatment or rinsing treatment, the heating (post-bake) treatment is carried out at a temperature of 100 to 160 ° C, preferably 110 to 140 ° C, preferably 1 to 30 minutes, more preferably 3 to 10 Minute.

As described above, a resist pattern can be obtained.

The support is not particularly limited and conventionally known ones can be used, and examples thereof include a substrate for electronic parts and a substrate having a predetermined wiring pattern formed thereon. More specifically, examples thereof include a metal substrate such as a silicon wafer, copper, chromium, iron, and aluminum, and a glass substrate. As the material of the wiring pattern, for example, copper, aluminum, nickel, gold and the like can be used.

For example, in the case of manufacturing an FPD, a large glass substrate is used, and a large glass substrate of 500 mm x 600 mm or more, particularly 550 mm x 650 mm or more is used. In the resist pattern forming method of this embodiment, even in the FPD production using such a large glass substrate, a resist film excellent in coatability and uniform in film thickness can be obtained.

As the support, an inorganic and / or organic film may be formed on the above-described substrate. As the inorganic film, an inorganic anti-reflection film (inorganic BARC) can be mentioned. Examples of the organic film include an organic antireflection film (organic BARC) and an organic film such as a lower organic film in the multilayer resist method.

Here, the multi-layer resist method is a method in which at least one organic film (lower organic film) and at least one resist film (upper resist film) are formed on a substrate, and a resist film It is a method of patterning an organic film, and it is said that a pattern of a high aspect ratio can be formed. That is, according to the multilayer resist method, since the required thickness can be secured by the lower organic film, the resist film can be made thinner and a pattern having a ghost aspect ratio can be formed finely.

In the multilayer resist method, a method of basically forming a two-layer structure of an upper resist film and a lower layer organic film (two-layer resist method), and a method of forming an intermediate layer (metal thin film or the like) Layer structure (a three-layer resist method).

The wavelength to be used for exposure is not particularly limited, and in the case of FPD production, arbitrary two or more kinds of mixed light selected from the group consisting of g line, h line and i line, or a single light of g line, h line or i line It is preferable to apply the exposure process used for the exposure light source.

An exposure process using any two or more kinds of mixed light selected from the group consisting of g-line, h-line and i-line as an exposure light source is an exposure process using g-line (436 nm), h-line (405 nm) Nm) of exposure light having a plurality of exposure wavelengths as an exposure light source. The mixed light including a plurality of exposure wavelengths may be any of two types of mixed light selected from the group consisting of g line, h line and i line, and mixed light of three kinds of g line, h line and i line And it is preferable that the latter is a mixed light of three kinds.

The work time in the exposure process tends to become longer as the substrate becomes larger, such as FPD. On the other hand, by making the exposure light source a mixed light including a plurality of exposure wavelengths as described above, it becomes possible to increase the intensity of the light source, thereby shortening the exposure time. The spectral intensity of each light ray can be appropriately selected depending on the type of the substrate and the like.

In the production of FPD and the like, this selective exposure is carried out using a mask in which a mask pattern for forming a resist pattern having different pattern dimensions is drawn, so that a resist pattern having a different pattern size can be simultaneously formed on a glass substrate.

For example, this selective exposure can be carried out by using a mask (reticle) on which a resist pattern forming mask pattern having a pattern size of 0.5 to 2.5 μm and a mask pattern for forming a resist pattern having a pattern size of 3 to 10 μm are drawn . Even when the patterns having different sizes are formed at the same time, according to the resist pattern forming method of the present invention, the excellent linearity effect is exerted.

In the step (4), the pre-pattern is heated (post-baked) after the development treatment or after the rinsing treatment. At this time, preferably, the pre-pattern is heated and flowed. That is, the pre-pattern is heated and the edge of the pre-pattern is rounded (so-called chamfering is performed). As a result, a resist pattern having a rounded edge can be formed.

The resist pattern forming method of this embodiment is useful when manufacturing a through electrode in the production of a liquid crystal display device used for an FPD such as a liquid crystal display or a plasma display.

For example, when the support has a metal layer on the outermost surface, a resist pattern is formed on the metal layer by the resist pattern forming method of this embodiment, a laminate of the metal layer and the resist pattern is produced, Subsequently, the laminate is subjected to a dry etching process (a part of the metal layer is removed by using the resist pattern as a mask), thereby forming a pattern of the metal layer. By using the pattern, the penetrating electrode is manufactured.

As the metal layer, for example, a layer containing Cu, Si, ITO (indium tin oxide), Mo, Al, SiN, CGS (Cotinuous Grain Silicon), IGZO (indium gallium gallium oxide)

The support may have a layer other than a metal layer (for example, an insulating layer or the like) on its outermost surface.

Further, according to the resist pattern forming method of the present embodiment, for example, in the resist pattern formation in the line and space, the post-baking process is carried out to form resist patterns of a shape in which the edge of the line- A good pattern can be formed. Thereby, after the dry etching process, a pattern composed of the metal layer in the space portion of the resist pattern and the metal layer in which the metal layer covered with the line portion of the resist pattern is well connected is formed.

The method of forming a resist pattern of the present invention, the method of forming a pattern made of a metal layer, and the method of manufacturing a penetrating electrode are preferable methods for a TFT array manufacturing process.

Example

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

&Lt; Preparation of resist composition &gt;

(Examples 1 to 9 and Comparative Examples 1 to 4)

Each component shown in Table 1 was mixed and dissolved, and then filtered using a membrane filter having a pore size of 0.2 탆 to prepare positive resist compositions of the respective examples.

In Table 1, the respective abbreviations have the following meanings respectively. The values in [] are the compounding amount (parts by mass).

(A1) -1: A novolak resin having a mass average molecular weight (Mw) of 4000, obtained by condensation reaction of oxalic acid and formaldehyde by adding an injection molar ratio of 60 mol% of p-cresol and 40 mol% of m- (A1). The molar ratio of the novolak resin after the preparation (reaction) was almost the same as the injection molar ratio.

(A2) -1: A novolak resin having a mass average molecular weight (Mw) of 20,000 obtained by condensation reaction by adding oxalic acid and formaldehyde to a mixture of 40 mol% of p-cresol and 60 mol% of m-cresol (A2). The molar ratio of the novolak resin after the preparation (reaction) was almost the same as the injection molar ratio.

(A2) -2: A novolak resin having a weight average molecular weight (Mw) of 4000, obtained by a condensation reaction by adding oxalic acid and formaldehyde to a mixture of an injection molar ratio of 40 mol% of p-cresol and 60 mol% of m- (A3). The molar ratio of the novolak resin after the preparation (reaction) was almost the same as the injection molar ratio.

(A2) -3: a mixture of oxalic acid, salicylaldehyde and formaldehyde in a molar ratio of 1/9 to a mixture of 40 mol% of p-cresol and 60 mol% of m-cresol, Novolac resin (A4) having an average molecular weight (Mw) of 20000. The molar ratio of the novolak resin after the preparation (reaction) was almost the same as the injection molar ratio.

(B) -1: a compound represented by the following formula (B) -1 (2,2'-dimethyl-4,4 '- (fluorene-9,9-diyl) diphenol).

(C) -1: a photosensitive component comprising a compound represented by the following formula (C) -1 (wherein D ¹ to D ⁴ are each a hydrogen atom or a 1,2-naphthoquinonediazide-5-sulfonyl group) ; The esterification reaction product (esterification ratio: 72.3%) of 1 mole of a compound in which all of D ¹ to D ⁴ in the formula (C) -1 are hydrogen atoms and 2.89 moles of 1,2-naphthoquinonediazide-5-sulfonic acid chloride.

(S) -1: mixed solvent of propylene glycol monomethyl ether acetate (PGMEA) and hexylene glycol (HG) in a mass ratio PGMEA / HG = 98.5 / 1.5.

(7)

<Evaluation>

Using the obtained positive resist composition, a resist pattern was formed by the following method. At that time, the shape of the resist pattern before and after the post-baking was evaluated.

&Lt; Formation of resist pattern, evaluation of resist pattern shape &

Step (1):

The positive resist composition was applied on a 6-inch Si wafer using a spinner (trade name: TR-6132U, manufactured by Tatsumo Corporation). Thereafter, the resist film was dried with a direct hot plate (DHP) at 110 DEG C for 90 seconds to form a resist film having a thickness of 1.5 mu m.

Step (2):

Subsequently, a mask pattern for reproducing a resist pattern (LS pattern) of 3.0 μm line and space was formed on the resist film using a mirror projection aligner (trade name: MPA-600 FA, manufactured by Canon Inc., NA = 0.083) Through the drawn test chart mask (reticle), selective exposure was performed at an exposure dose capable of reproducing LS patterns having a focus of 0 占 퐉 and 3.0 占 퐉 in dimensions.

Step (3):

Subsequently, the substrate was contacted with a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (TMAH) at 23 占 폚 for 65 seconds, rinsed for 30 seconds, and spin-dried.

After the spin drying, the shape of the obtained pre-pattern was observed with an SEM (scanning electron microscope).

Step (4):

Subsequently, heating (postbaking) was performed at 130 DEG C for 5 minutes to finally obtain a resist pattern.

After the post-baking, the shape of the obtained resist pattern was observed with an SEM (scanning electron microscope).

Table 2 shows the results of SEM observation of the pre-pattern shape before post-baking in step (4) and the post-baked resist pattern shape. Each pattern shape was evaluated based on the following evaluation criteria.

[Evaluation criteria of pre-pattern shape before post-baking]

?: Good taper shape (shape that does not generate shape abnormality at the time of flow).

X: The square formation was excessively high or the pattern was excessively laid.

[Evaluation Criteria of Resist Pattern Shape after Post Baking]

Fig. 1 shows a typical shape model of the post-baked resist pattern 10 corresponding to the following evaluation (?,?, X).

A: No edge or step, and roundish and good shape.

A: There was no step, but it was a slightly good shape with a little edge 12 remaining.

X: Inadequate shape with a step 14 (rabbit ears) on the surface of the resist pattern 10.

&Lt; Formation of resist pattern, evaluation of residual film property of resist film &

A resist pattern was formed in the same manner as in the formation of the resist pattern by the above steps (1) to (4), and the film thickness of the resist pattern after post-baking / the film thickness of the resist film before development was measured, Respectively.

The film thickness of the resist pattern after post-baking and the film thickness of the resist film before development were measured using a stylus-type surface shape measuring instrument (Dektak 3st, manufactured by ULVAC Co., Ltd.).

Using the residual film ratio as an index, the residual film property of the resist film was evaluated based on the following evaluation criteria. The results are shown in Table 2.

[Evaluation Criteria of Residual Film Property of Resist Film]

⊚: Remaining film rate is 95% or more.

?: Remaining film ratio of 90% or more and less than 95%.

X: Residual film ratio is less than 90%.

From the results shown in Table 2, it can be seen that the positive resist compositions of Examples 1 to 9 to which the present invention is applied do not well cause a defective shape due to post-baking.

10: Resist pattern
12: Edge
14: Step

Claims (13)

(A), a phenol compound component (B), and a photosensitive component (C) containing a novolak resin containing a p-cresol repeating unit (a1) and an m- A positive resist composition comprising:
The novolak resin is a novolac resin having a novolak resin (A1) / repeating unit (a2) = 6/4 to 9/1 in which the mixing ratio (molar ratio) of the repeating unit (a1) And a novolak resin (A2) having a repeating unit (a1) / a repeating unit (a2) = 1/9 to 4/6. The method according to claim 1,
Wherein the novolak resin (A1) / novolak resin (A2) = 5/5 to 9/1 is a blend ratio (mass ratio) of the novolak resin (A1) and the novolak resin (A2). 3. The method according to claim 1 or 2,
Wherein the novolak resin (A1) has a mass average molecular weight of 2000 to 8000 and the novolak resin (A2) has a mass average molecular weight of 2000 to 30000. 4. The method according to any one of claims 1 to 3,
Wherein the novolak resin (A2) contains a group represented by the following formula (x1) and a group represented by the formula (x2).
[Chemical Formula 1]

[In the formula, * indicates a binding hand.] 5. The method according to any one of claims 1 to 4,
Wherein the phenolic compound component (B) is a compound represented by the following general formula (b1).
(2)

Wherein R ¹ and R ² are each independently a hydroxyl group or an alkyl group having 1 to 5 carbon atoms, and n 1 and n 2 are each independently an integer of 0 to 3.] 6. The method according to any one of claims 1 to 5,
Wherein the photosensitive component (C) is a compound represented by the following general formula (c1-1).
(3)

In formula (c1-1), D ¹ to D ⁴ each independently represent a hydrogen atom or a 1,2-naphthoquinonediazide-5-sulfonyl group, and at least one of D ¹ to D ⁴ represents 1 , 2-naphthoquinonediazide-5-sulfonyl group. 7. The method according to any one of claims 1 to 6,
Wherein the content of the phenol compound component (B) is 3 to 25 parts by mass based on 100 parts by mass of the alkali-soluble resin component (A). 8. The method according to any one of claims 1 to 7,
Wherein the content of the photosensitive component (C) is 15 to 40 parts by mass based on 100 parts by mass of the total of the alkali-soluble resin component (A) and the phenol compound component (B). 9. The method according to any one of claims 1 to 8,
A positive resist composition which is a resist composition for producing a flat panel display. A step (1) of forming a resist film on the support using the positive resist composition according to any one of claims 1 to 9,
A step (2) of exposing the resist film,
A step (3) of developing the exposed resist film to form a pre-pattern, and
(4) heating the pre-pattern to form a resist pattern. 11. The method of claim 10,
Wherein the pre-pattern is heated and flowed in the step (4). A step of forming a resist pattern on the metal layer by the resist pattern forming method according to claim 11 to obtain a laminate of a metal layer and a resist pattern,
And a step of forming a pattern of the metal layer by performing a dry etching treatment on the laminate. A method of manufacturing a through-hole electrode characterized by using a method of forming a pattern made of the metal layer according to claim 12.

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