TW201642024A - Positive-type photosensitive resin composition for production of microlens pattern - Google Patents

Abstract

The present invention relates to a positive-type photosensitive resin composition for use in the formation of microlens patterns, having desirable resolution and wide flow margin, a method for fabricating a microlens pattern using the same, and a method for producing a microlens. The positive-type photosensitive resin composition for use in the formation of microlens patterns, comprises: a resin (A) which has an acid dissociable dissolution inhibiting group and whose solubility in a base increases through the action of acid; a compound (B) having at least 2 vinyloxy groups; and a photo acid generator (C), wherein the resin (A) includes a resin (A1) that includes a repeating unit (a1) which is derived from hydroxystyrene and a repeating unit (a2) derived from hydroxystyrene having a hydrogen atom in at least one hydroxyl group is substituted with an acid dissociable dissolution inhibiting group.

Description

Positive photosensitive resin composition for manufacturing microlens pattern

The present invention relates to a positive photosensitive resin composition for producing a microlens pattern, a method for producing a microlens pattern using the composition, and a method for producing a microlens.

In the past, solid-state imaging elements were used in cameras and cameras. This solid-state imaging device uses a CCD (charge-coupled device) image sensor or a CMOS (complementary metal-oxide semiconductor) image sensor. A fine condenser lens (hereinafter referred to as a microlens) for increasing the concentration of light is provided in the image sensor.

The microlens is formed, for example, by an etching method using a positive photosensitive resin composition. Specifically, after forming a positive photosensitive resin composition layer on the lens material layer using a positive photosensitive resin composition, this is selectively exposed. Then, after the exposed portion is removed by development, the positive photosensitive resin composition layer is fluidized by heat treatment to form a mask layer having a microlens pattern. Then, the lens material layer and the mask layer are dry-etched, and the microlens is obtained by transferring the shape of the microlens pattern to the lens material layer. In the conventional positive photosensitive resin composition for producing a microlens pattern for use in the above-mentioned mask layer, for example, an acrylic or phenolic positive resist material is used (Patent Document 1).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2013-117662

As described above, the positive photosensitive resin composition for producing a microlens pattern requires excellent resolution and a wide flow margin (a temperature range in which a good microlens pattern can be formed), but the conventional microlens pattern is manufactured. With a positive photosensitive resin composition, these characteristics are insufficient.

The present invention has been made in view of the facts of the present invention, and an object of the present invention is to provide a positive-type photosensitive resin composition for manufacturing a microlens pattern having excellent resolution and a wide flow margin, and to use the composition. A method of manufacturing a microlens pattern and a method of manufacturing a microlens.

The present inventors have found that a specific resin having an acid dissociable dissolution inhibiting group and a solubility of an alkali by an action of an acid and a compound having at least two ethyleneoxy groups can be used to solve the above problems. invention. Specifically, the present invention provides the following.

The first aspect of the present invention is a positive photosensitive resin composition comprising: a resin (A) having an acid dissociable dissolution inhibiting group and having an increased solubility to an alkali by an action of an acid, having at least 2 A positive photosensitive resin composition for producing a fluorinated compound (B) and a photoacid generator (C), wherein the resin (A) contains a constituent unit derived from hydroxystyrene (a1) And a resin (A1) constituting the unit (a2) in which a hydrogen atom of at least one hydroxyl group in a constituent unit derived from hydroxystyrene is substituted with a group containing an acid dissociable dissolution inhibiting group.

A second aspect of the present invention is a method for producing a microlens pattern comprising the step of forming a positive photosensitive resin composition of a positive photosensitive resin composition layer using the positive photosensitive resin composition described above. a layer forming step of exposing the positive photosensitive resin composition layer to an exposure step, a developing step of developing the exposed positive photosensitive resin composition layer after exposure, and the positive photosensitive property after development The heating step of heating the resin composition layer.

A third aspect of the present invention provides a method for producing a microlens, comprising the step of: laminating a positive photosensitive resin composition layer on a lens material layer using the positive photosensitive resin composition; a photosensitive resin composition layer laminating step, an exposure step of selectively exposing the positive photosensitive resin composition layer, and a developing step of developing the exposed positive photosensitive resin composition layer after exposure, and developing the image The positive photosensitive resin composition layer is heated to form a mask layer forming step having a mask layer of a microlens pattern, and dry etching the lens material layer and the mask layer to convert the shape of the microlens pattern Printed to the above lens material The shape transfer step of the layer.

According to the present invention, it is possible to provide a positive photosensitive resin composition for producing a microlens pattern having excellent resolution and a wide flow margin, and a method for producing a microlens pattern using the composition and micro The method of manufacturing the lens.

[Formation of the Invention] <Positive Photosensitive Resin Composition for Microlens Pattern Manufacturing>

The positive photosensitive resin composition for producing a microlens pattern of the present invention contains a resin (A) having an acid dissociable dissolution inhibiting group and having an increased solubility to an alkali by an action of an acid, and having at least 2 ethylene oxides. a compound (B) and a photoacid generator (C), wherein the resin (A) contains at least one hydroxyl group having a constituent unit derived from hydroxystyrene (a1) and a constituent unit derived from hydroxystyrene The resin (A1) constituting the unit (a2) in which a hydrogen atom is substituted with a group containing an acid dissociable dissolution inhibiting group. When the positive photosensitive resin composition is manufactured by an etching method, it is suitable for forming a mask layer having a microlens pattern. Hereinafter, each component contained in the above-mentioned positive photosensitive resin composition will be described in detail.

[Resin (A) having an acid dissociable dissolution inhibiting group and increasing solubility in alkali by an action of an acid]

The resin (A) having an acid dissociable dissolution inhibiting group and having an increased solubility in alkali by an action of an acid contains a constituent unit derived from hydroxystyrene (a1) and a constituent unit derived from hydroxystyrene A resin (A1) constituting the unit (a2) in which at least one hydrogen atom of a hydroxyl group is substituted with a group containing an acid dissociable dissolution inhibiting group. The resin (A) may be used singly or in combination of two or more.

When the resin (A) contains the resin (A1) having the constituent unit (a1) and the constituent unit (a2), the positive photosensitive resin composition obtained is excellent in resolution, and it is easy to ensure a wide flow margin.

The constituent unit (a1) is, for example, a constituent unit represented by the following general formula (a1-1). In addition, the constituent unit (a2) may be, for example, a constituent unit represented by the following general formula (a2-1).

(wherein R ^a1 and R ^a3 independently represent a hydrogen atom, an alkyl group, a halogen atom, or an alkyl group substituted with a halogen atom, R ^a2 and R ^a5 independently represent an alkyl group, and R ^a4 represents an acid dissociable dissolution inhibiting group, p And r independently represent integers from 1 to 5, and q, s, and t independently represent integers from 0 to 4, but p+q and r+s+t are independently integers from 1 to 5.

In the general formula (a1-1), R ^a1 and R ^a3 represent a hydrogen atom, an alkyl group, a halogen atom or an alkyl group substituted by a halogen atom. The alkyl group of R ^a1 and R ^a3 is an alkyl group having 1 to 5 carbon atoms, preferably a linear or branched alkyl group, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, and an n-butyl group. Base, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, and the like. Industrially preferred is methyl. The halogen atom may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and particularly preferably a fluorine atom. The alkyl group substituted by a halogen atom is a part or all of a hydrogen atom of one or more of the alkyl groups having 1 to 5 carbon atoms, which is substituted by a halogen atom. In the present invention, it is preferred that all of the hydrogen atoms are halogenated. The alkyl group substituted by a halogen atom is preferably a linear or branched alkyl group substituted by a halogen atom, particularly preferably a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a nonafluorobutyl group or the like. The fluorinated alkyl group is preferably a trifluoromethyl group (-CF ₃ ). R ^a1 and R ^{a3 are} preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.

The alkyl group having 1 to 5 carbon atoms of R ^a2 and R ^a5 may be the same as the alkyl group of R ^a1 and R ^a3 . q, s, and t are independently integers from 0 to 4. Among these, q, s, and t are preferably 0 or 1, and industrially preferably 0. The substitution position of R ^a2 is a case where q is 1, and may be any of the o-position, the m-position, and the p-position, and q is an integer of 2 to 4, and any substitution position may be combined. The substitution position of R ^a5 is a case where t is 1, and may be any of the o-position, the m-position, and the p-position, and t is an integer of 1 to 4, and any substitution position may be combined. p and r represent an integer of 1 to 5, preferably an integer of 1 to 3, preferably 1. When the substitution position of the hydroxyl group is p and s is 1, it may be any of the o-position, the m-position, and the p-position, but it is easily available and has a low price, preferably a p-position. Further, in the case where p is an integer of 2 to 5 and s is an integer of 2 to 4, any substitution position may be combined.

The acid dissociable dissolution inhibiting group represented by R ^a4 , for example, a group represented by the following formula (a2-1-1), a group represented by the following formula (a2-1-2), and a carbon number of 1 to 6 A linear, branched, or cyclic alkyl group, a vinyloxyethyl group, a tetrahydropyranyl group, a tetrafuranyl group, or a trialkylcarbenyl group.

In the above formulae (a2-1-1) and (a2-1-2), R ^a6 and R ^a7 independently represent a hydrogen atom or an alkyl group, and R ^a8 and R ^a10 independently represent an alkyl group or a cycloalkyl group, and R ^a9 represents a single A bond or an alkyl group, but at least two of R ^a6 , R ^a7 , and R ^{a8 are} bonded to each other to form a ring.

The alkyl group represented by R ^a6 or R ^a7 may, for example, be a linear or branched alkyl group having 1 to 6 carbon atoms. The alkyl group represented by R ^a8 may, for example, be a linear or branched alkyl group having 1 to 10 carbon atoms, and a cycloalkyl group represented by R ^a8 may, for example, be a cycloalkyl group having 3 to 10 carbon atoms. The alkylene group represented by R ^a9 may, for example, be an alkylene group having 1 to 3 carbon atoms. Examples of the alkyl group represented by R ^a10 include a linear or branched alkyl group having 1 to 6 carbon atoms, and a cycloalkyl group represented by R a ¹⁰ , and examples thereof include a cycloalkyl group having 3 to 6 carbon atoms.

Examples of the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group. Pentyl, isopentyl, neopentyl. Further, examples of the cycloalkyl group include a cyclopentyl group and a cyclohexyl group. The above alkylene group may, for example, be a methylene group, an ethylidene group, a methylmethylene group, a propyl group, an exopropyl group or an ethylmethylene group.

Here, the acid dissociable dissolution inhibiting group represented by the above formula (a2-1-1), specifically, for example, methoxyethyl, ethoxyethyl, n-propoxyethyl or the like Propoxyethyl, n-butoxyethyl, isobutoxyethyl, tert-butoxyethyl, cyclohexyloxyethyl, methoxypropyl, ethoxypropyl, 1- Methoxy-1-methyl-ethyl, 1-ethoxy-1-methylethyl and the like. In addition, the acid dissociable dissolution inhibiting group represented by the above formula (a2-1-2) may, for example, be a tert-butoxycarbonyl group or a tert-butoxycarbonylmethyl group. Further, examples of the trialkylcarbenyl group include those having 1 to 6 carbon atoms of each alkyl group such as trimethylmethanealkyl or tri-tert-butyldimethylformamidin.

Each of the constituent units (a1) and (a2) may be used alone or in combination of two or more.

In the resin (A1), the total ratio of the constituent units (a1) and (a2) is preferably 10 to 100 mol%, more preferably 30 to 100 mol%, based on the total constituent unit of the constituent resin (A1). %, more preferably 50~100% by mole, especially preferably 70~100% by mole, and most preferably 100% by mole. When the ratio is within the above range, the positive photosensitive resin composition obtained tends to be more excellent in resolution, and it is easy to secure a wider flow margin, and the balance with other constituent units is good.

In the total of the constituent units (a1) and (a2), the ratio of the constituent unit (a2) (that is, the protection ratio of hydroxystyrene) is preferably 10 to 60 m. %, more preferably 20 to 40% by mole. When the protective ratio of the hydroxystyrene is within the above range, the obtained positive photosensitive resin composition is more likely to be excellent in resolution, and it is easy to secure a wider flow margin.

(other constituent units)

The resin (A1) is in addition to the constituent units (a1) and (a2). It may also contain other constituent units other than the constituent units (a1) and (a2). Specific examples of the other constituent units include the following constituent units (a3) and (a4).

. Constituent unit (a3)

The constituent unit (a3) is a constituent unit derived from styrene. By including the constituent unit (a3) and adjusting the content thereof, the solubility of the resin (A1) in the alkali developing solution may be adjusted, whereby the alkali solubility of the thick film resist film may be controlled. It is also possible to increase the shape of the situation.

Here, "styrene" means a substituent in which a hydrogen atom at the α position of styrene and a narrow styrene is substituted with a halogen atom, an alkyl group, a halogenated alkyl group or the like, and contains the other substituents. The concept of derivatives. The "constituting unit derived from styrene" means a constituent unit composed of ethylene double bond cracking of styrene. The hydrogen atom of the phenyl group of styrene may also be substituted with a substituent such as a lower alkyl group (for example, an alkyl group having 1 to 5 carbon atoms).

The constituent unit (a3) has, for example, a constituent unit represented by the following general formula (a3-1).

In the formula, R represents a hydrogen atom, an alkyl group, a halogen atom or an alkyl group substituted by a halogen atom, R ⁷ represents an alkyl group having 1 to 5 carbon atoms, and r represents an integer of 0 to 3.

R may be, for example, the same as those exemplified above for R ^a1 and R ^a3 . R ⁷ may, for example, be the same as those exemplified above for R ^a2 and R ^a5 .

r is an integer from 0 to 3. Among these, r is preferably 0 or 1, and industrially preferably 0.

The substitution position of R ⁷ may be any of the o-position, the m-position, and the p-position, and r may be 2 or 3 in the case where r is 1, and any substitution position may be combined.

The constituent unit (a3) may be used alone or in combination of two or more.

In the resin (A1), the ratio of the constituent unit (a3) is preferably from 0 to 90 mol%, more preferably from 0 to 70 mol%, more preferably from 0 to 90 mol%, more preferably from the total constituent unit of the constituent resin (A1). 0~50% by mole, especially preferably 0~30% by mole, and most preferably 0% by mole. When the above ratio is within the above range, the balance with other constituent units tends to be good. The lower limit of the above ratio is relative to the constituent tree The total constituent unit of the fat (A1) is preferably 1 mol%, more preferably 3 mol%, and particularly preferably 5 mol%. When the lower limit is the above value, the effect obtained by having the constituent unit (a3) is likely to be improved.

. Constituent unit (a4)

The constituent unit (a4) is a constituent unit derived from an acrylate having an alcoholic hydroxyl group. By having such a constituent unit (a4), there is a case where the effect of the present invention is further improved.

The constituent unit (a4) is preferably a constituent unit containing a chain or cyclic alkyl group having an alcoholic hydroxyl group. That is, the constituent unit (a4) is preferably a constituent unit derived from an acrylate having a chain or cyclic alkyl group having an alcoholic hydroxyl group.

When the constituent unit (a4) has a constituent unit derived from an acrylate having a cyclic alkyl group having an alcoholic hydroxyl group (hereinafter sometimes referred to simply as "a constituent unit having a cyclic alkyl group having a hydroxyl group"), In the case where the image is improved, there is also a case where the etching resistance is improved.

In addition, when the constituent unit (a4) has a constituent unit derived from an acrylate having a chain alkyl group having an alcoholic hydroxyl group (hereinafter sometimes referred to simply as "a constituent unit having a hydroxyl group-containing chain alkyl group"), When the hydrophilicity of the entire component (A) is improved, the affinity with the developer is improved, so that the resolution is improved.

. . a constituent unit having a cyclic alkyl group having a hydroxyl group

A constituent unit having a cyclic alkyl group having a hydroxyl group, and examples thereof include propylene. A constituent unit of a cyclic alkyl group having a hydroxyl group bonded to an ester group [-C(O)O-] of the acid ester. Here, the "hydroxyl-containing cyclic alkyl group" means a group having a hydroxyl group bonded to a cyclic alkyl group.

Preferably, the hydroxyl group is, for example, 1 to 3 bonds, and the bonding is preferably one.

The cyclic alkyl group may be a single ring or a polycyclic ring, but is preferably a polycyclic group. Further, the number of carbon atoms of the cyclic alkyl group is preferably from 5 to 15.

Specific examples of the cyclic alkyl group include the following.

The monocyclic cyclic alkyl group may, for example, be a group obtained by removing one to four hydrogen atoms from a cycloalkane. More specifically, the monocyclic cyclic alkyl group may, for example, be a group obtained by removing one to four hydrogen atoms from a cycloalkane such as cyclopentane or cyclohexane. Among these, it is preferably Cyclohexyl.

The polycyclic cyclic alkyl group may, for example, be a group obtained by removing one to four hydrogen atoms from a polycyclic alkane such as a bicycloalkane, a tricycloalkane or a tetracycloalkane. More specifically, for example, a group obtained by removing one to four hydrogen atoms from a polycyclic alkane such as adamantane, norbornane, isodecane, tricyclodecane or tetracyclododecane may be mentioned.

Further, such a cyclic alkyl group is suitably used, for example, as a resin for forming a photoresist composition for an ArF excimer laser process, which is proposed as an acid dissociation dissolution inhibiting group. Among these, cyclohexyl, adamantyl, norbornyl, and tetracyclododecyl are preferable because they are industrially easy to obtain.

Among the above-exemplified monocyclic and polycyclic groups, a cyclohexyl group and an adamantyl group are preferred, and an adamantyl group is particularly preferred.

Specific examples of the constituent unit having a cyclic alkyl group having a hydroxyl group are preferably, for example, a constituent unit (a4-1) represented by the following general formula (a4-1).

In the formula, R represents a hydrogen atom, an alkyl group, a halogen atom, or an alkyl group substituted by a halogen atom, and s is an integer of 1 to 3.

R may be, for example, the same as those exemplified above for R ^a1 and R ^a3 .

s is an integer from 1 to 3, and most preferably 1.

The bonding position of the hydroxyl group is not particularly limited, and it is preferred that the hydroxyl group is bonded to the position of the adamantyl group at the 3-position.

. . a constituent unit having a hydroxyl group-containing chain alkyl group

The constituent unit of the chain-like alkyl group having a hydroxyl group may, for example, be a constituent unit in which a chain hydroxyalkyl group is bonded to an ester group of acrylate [-C(O)O-]. Here, the "chain hydroxyalkyl group" means a group in which a part or all of a hydrogen atom in a chain (linear or branched) alkyl group is substituted with a hydroxyl group.

The constituent unit having a hydroxyl group-containing chain alkyl group is particularly preferably a constituent unit (a4-2) represented by the following general formula (a4-2).

In the formula, R is the same as above, and R ⁸ is a chain hydroxyalkyl group. ]

R may be the same as those exemplified above for R ^a1 and R ^a3 .

a hydroxyalkyl group of R ⁸ , preferably a hydroxyalkyl group having 1 to 10 carbon atoms, more preferably a hydroxyalkyl group having 2 to 8 carbon atoms, more preferably a linear hydroxyalkyl group having 2 to 4 carbon atoms; .

The number of the hydroxyl groups in the hydroxyalkyl group and the bonding position are not particularly limited, and usually the number of the hydroxyl groups is one, and the bonding position is preferably the terminal of the alkyl group.

The constituent unit (a4) may be used alone or in combination of two or more.

In the resin (A1), the ratio of the constituent unit (a4) is preferably from 0 to 90 mol%, more preferably from 0 to 70 mol%, more preferably from 0 to 90 mol%, more preferably from the total constituent unit of the constituent resin (A1). 0~50% by mole, especially good for 0~30% by mole, best It is 0% by mole. When the above ratio is within the above range, the balance with other constituent units tends to be good. The lower limit of the above ratio is preferably 1 mol%, more preferably 3 mol%, and particularly preferably 5 mol%, based on the total constituent unit of the constituent resin (A1). When the lower limit is the above value, the effect obtained by having the constituent unit (a4) is easily improved.

The resin (A1) may contain other constituent units (a5) other than the above-described constituent units (a1) to (a4) within a range not impairing the effects of the present invention.

The constituent unit (a5) is not particularly limited as long as it is not classified into the other constituent units (a1) to (a4), and may be used for ArF excimer laser or KrF positive type. Resins for molecular lasers (preferably for KrF excimer lasers) and the like are conventionally known.

The resin (A1) may be used alone or in combination of two or more.

In the component (A), the ratio of the resin (A1) is preferably from 50 to 100% by mass, more preferably from 80 to 100% by mass, most preferably 100% by mass, in order to obtain the effect of the present invention.

The resin (A1) preferably contains a resin (A2) having a constituent unit represented by the following formula (a1-1) and a constituent unit represented by the following formula (a2-1).

(wherein, R ^a1 to R ^a5 and p~t are as described above.)

Since the resin (A1) contains the resin (A2), the obtained positive photosensitive resin composition is more likely to be excellent in resolution, and it is easy to secure a wider flow margin.

The resin (A2) may be used alone or in combination of two or more.

In the resin (A1), the ratio of the resin (A2) is preferably from 50 to 100% by mass, more preferably from 80 to 100% by mass, most preferably 100% by mass, in order to obtain the effect of the present invention.

The resin (A2) contains a resin having a constituent unit represented by the above formula (a1-1) and a constituent unit represented by the following formula (a2-2) and/or a constituent unit represented by the following formula (a2-3) (A3) ) is better.

(wherein R ^a3 , R ^a5 to R ^a10 , r, s, and t are as described above.)

When the resin (A2) contains the resin (A3), the obtained positive photosensitive resin composition is more likely to be excellent in resolution, and it is easy to secure a wider flow margin.

The resin (A3) may be used alone or in combination of two or more.

In the resin (A2), the ratio of the resin (A3) is preferably from 50 to 100% by mass, more preferably from 80 to 100% by mass, most preferably 100% by mass, in order to obtain the effect of the present invention.

The resin (A3) includes a constituent unit represented by the above formula (a1-1), a resin (A4) represented by the above formula (a2-2), and/or a constituent unit represented by the above formula (a1-1). The resin (A5) which is a constituent unit represented by the above formula (a2-3) is preferred.

When the resin (A3) contains the resin (A4) and/or the resin (A5), the positive photosensitive resin composition obtained tends to be more excellent in resolution, and it is easy to ensure a wider flow margin.

In particular, in the case where the resin (A3) contains both the resin (A4) and the resin (A5), it is preferable because it has both high resolution and a wide flow margin.

Each of the resin (A4) and the resin (A5) may be used alone or in combination of two or more.

In the resin (A3), the ratio of the total of the resins (A4) and (A5) is preferably from 50 to 100% by mass, more preferably from 80 to 100% by mass, most preferably 100% by mass, in order to obtain the effect of the present invention.

The amount of the resin (A4) is preferably 60 to 90 mol%, more preferably 70 to 80 mol%, based on the total of the resin (A4) and the resin (A5). When the amount of the resin (A4) is within the above range, the obtained positive photosensitive resin composition It is easy to become more excellent in resolving, and in particular, it is easy to ensure a wider flow margin.

The mass average molecular weight (Mw) of the resin (A1) is preferably from 5,000 to 30,000. The same applies to the mass average molecular weight of the resins (A2) and (A3). When the mass average molecular weight is within the above range, the resolution, heat resistance, and fluidity of the obtained positive photosensitive resin composition tend to be good. In the present specification, the mass average molecular weight means a polystyrene equivalent obtained by gel permeation chromatography (GPC).

The mass average molecular weight of the resin (A4) is preferably from 15,000 to 30,000, more preferably from 17,000 to 25,000. When the mass average molecular weight is 15,000 or more, the positive photosensitive resin composition obtained tends to improve heat resistance, and the fluidity is not excessively high, so that it is easy to secure a wide flow margin. In addition, when the mass average molecular weight is 30,000 or less, the obtained positive photosensitive resin composition is likely to be excellent in resolution.

The mass average molecular weight of the resin (A5) is preferably from 5,000 to 15,000, more preferably from 7,000 to 10,000. When the mass average molecular weight is within the above range, the obtained positive photosensitive resin composition is likely to be excellent in heat resistance and fluidity.

In the present invention, as the component (A), in addition to the resin (A1), a PHS-based resin or an acrylic resin may be contained as a chemically broadened positive resist as a component of the component (A). A resin used with a resin.

The mass average molecular weight (Mw) of the resin (A) is preferably from 5,000 to 30,000. When the mass average molecular weight is within the above range, the obtained The positive photosensitive resin composition is likely to be excellent in resolution, heat resistance, and fluidity.

In the positive photosensitive resin composition of the present invention, the content of the component (A) may be adjusted in accordance with the thickness of the resist film to be formed.

[Compound (B) having at least 2 ethyleneoxy groups]

The compound (B) having at least two ethyleneoxy groups is not particularly limited as long as it is a compound having two or more vinyl ether groups in which an oxygen atom of a vinyloxy group (CH ₂ =CH-O-) is bonded to a carbon atom. Specially limited. By containing such a compound, the positive-type photosensitive resin composition obtained is more excellent in resolution, and it is easy to ensure a wide flow margin. The component (B) may be used singly or in combination of two or more.

The compound (B) having at least two ethyleneoxy groups is presumed to exert the above effects by acting as a crosslinking agent for the component (A). That is, the compound (B) having at least two ethyleneoxy groups is subjected to a crosslinking reaction with the component (A) by heating during prebaking, and an alkali-insoluble resist layer is formed on the entire substrate. Then, at the time of exposure, it is presumed that the cross-linking is decomposed by the action of the acid generated by the component (B), the exposed portion becomes alkali-soluble, and the unexposed portion is not changed to alkali-insoluble, so that the dissolution contrast is improved. Further, it is presumed that the post-baking is further cross-linked with the resin (A) to increase the flow margin.

The compound (B) having at least two ethylene-oxy groups, and the like, are arbitrarily selected from the group consisting of JP-A-6-148889, JP-A-6-230574, and the like. In particular, consider the shape of the resisting agent due to thermal crosslinkability and acid decomposition. In the case of the characteristics of the contrast between the exposed portion and the unexposed portion, the partial or total hydrogen atom of one or more of the hydroxyl groups of the alcohol represented by the following general formula (f-2) is substituted with a vinyl group to carry out etherification. The compound is preferred.

Rb-(OH) _b (f-2)

In the formula, Rb is a group obtained by removing a hydrogen atom from a linear, branched or cyclic alkane, and may have a substituent. Further, the alkane may contain an oxygen bond (ether bond). b means 2, 3, or 4.

Specific examples thereof include ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,3-butylene glycol divinyl ether, tetramethylene glycol divinyl ether, and neopentyl Diol divinyl ether, trimethylolpropane trivinyl ether, trimethylolethane trivinyl ether, hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, four Ethylene glycol divinyl ether, pentaerythritol divinyl ether, pentaerythritol trivinyl ether, cyclohexane dimethanol divinyl ether, and the like.

The compound (B) having at least two ethyleneoxy groups is preferably represented by the following general formula (f-3).

CH ₂ =CH-OR ²⁷ -O-CH=CH ₂ (f-3)

In the formula (f-3), R ²⁷ is a branched or linear alkyl group having 1 to 10 carbon atoms or a group represented by the following general formula (f-4). R ²⁷ may have a substituent. Further, the main chain of R ²⁷ may contain an oxygen bond (ether bond).

In the general formula (f-4), R ^{28 is} each independently a branched or linear alkyl group having 1 to 10 carbon atoms which may have a substituent, and the alkylene group may have an oxygen bond in the main chain. (ether bond). c is independently 0 or 1.

R ^{27 is} preferably -C ₄ H ₈ -, -C ₂ H ₄ OC ₂ H ₄ -, -C ₂ H ₄ OC ₂ H ₄ OC ₂ H ₄ -, a group represented by the general formula (f-4) And wherein, preferably, it is a group represented by the general formula (f-4), particularly, R ²⁸ is a C 1 alkyl group (that is, a methylene group), and c is 1 by a general formula (f- 4) The base shown is preferred.

The compound represented by the general formula (f-3) is preferably cyclohexanediol divinyl ether [hereinafter abbreviated as CHDVE].

In the positive photosensitive resin composition of the present invention, the content of the component (B) is 100 parts by mass relative to the component (A) from the viewpoint of easily improving the resolution and flow margin of the positive photosensitive resin composition obtained. It is preferably 0.1 to 15 parts by mass, more preferably 1 to 8 parts by mass.

[Photoacid generator (C)]

The photoacid generator (C) used in the present invention is not particularly limited as long as it is a compound which generates an acid by irradiation with active light or radiation. The component (C) may be used alone or in combination of two or more.

The component (C) is preferably a photoacid generator of the first to fifth aspects described below. Hereinafter, for the more suitable ones of the components (C), the first to the first Five aspects to illustrate.

The first aspect of the component (C) includes a compound represented by the following formula (c1).

In the above formula (c1), X ^1c represents a sulfur atom or an iodine atom of the valence g, and g is 1 or 2. h represents the number of repeating units of the structure in parentheses. R ^1c is an organic group bonded to X ^1c , and represents an aryl group having 6 to 30 carbon atoms, a heterocyclic group having 4 to 30 carbon atoms, an alkyl group having 1 to 30 carbon atoms, and an alkenyl group having 2 to 30 carbon atoms. Or an alkynyl group having 2 to 30 carbon atoms, and R ^1c may also be selected from an alkyl group, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, or an anthracene group. Oxyl, arylthio, alkylthio, aryl, heterocyclic, aryloxy, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, alkoxy At least one of a group of a group, an amine group, a cyano group, a nitro group, and a halogen group. The number of R ^1c is g+h(g-1)+1, and R ^1c may be the same or different from each other. Further, two or more R ^1c may be directly or mutually via -O-, -S-, -SO-, -SO ₂ -, -NH-, -NR ^2c -, -CO-, -COO-, - CONH-, an alkylene group having a carbon number of 1 to 3, or a phenyl group to bond, may also form a ring structure containing X ^1c . R ^2c is an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms.

X ^2c is a structure represented by the following formula (c2).

In the above formula (c2), X ^4c represents an alkylene group having 1 to 8 carbon atoms, an extended aryl group having 6 to 20 carbon atoms, or a divalent group having a heterocyclic compound having 8 to 20 carbon atoms, and X ^4c may also be Selecting an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, a hydroxyl group, a cyano group, a group of a nitro group, and at least 1 group of a halogen group Replaced by species. X ^5c represents -O-, -S-, -SO-, -SO ₂ -, -NH-, -NR ^2c -, -CO-, -COO-, -CONH-, alkylene having 1 to 3 carbon atoms Or stretch phenyl. h represents the number of repeating units of the structure in parentheses. The h+1 X ^4c and the h X ^5c may be the same or different. R ^2c is the same as defined above.

X ^3c- is a counter ion of a hydrazine, and a fluorinated alkyl fluorophosphate anion represented by the following formula (c17) or a borate anion represented by the following formula (c18) is mentioned.

In the above formula (c17), R ^3c represents an alkyl group in which 80 mol% or more of a hydrogen atom is substituted by a fluorine atom. j indicates the number, which is an integer from 1 to 5. The j R ^3c may be the same or different.

In the above formula (c18), R ^4c to R ^7c each independently represent a fluorine atom or a phenyl group, and part or all of a hydrogen atom of the phenyl group may be selected from at least a group consisting of a fluorine atom and a trifluoromethyl group. 1 substitution.

Examples of the phosphonium ion in the compound represented by the above formula (c1) include triphenylsulfonium, tris-p-methylphenylphosphonium, 4-(phenylthio)phenyldiphenylphosphonium, and bis[4-(diphenyl). Mercapto)phenyl]thioether, bis[4-{bis[4-(2-hydroxyethoxy)phenyl]indolyl}phenyl] sulfide, double {4-[bis(4-fluorophenyl)鋶]phenyl]thioether, 4-(4-benzylidene-2-chlorophenylthio)phenylbis(4-fluorophenyl)anthracene, 7-isopropyl-9-sideoxy- 10-thia-9,10-dihydroinden-2-yldi-p-tolylhydrazine, 7-isopropyl-9-oxooxy-10-thia-9,10-dihydroindole-2- Diphenyl hydrazine, 2-[(diphenyl)indenyl]thioxanthone, 4-[4-(4-tert-butylbenzylidene)phenylthio]phenyldi-p-tolyl Bismuth, 4-(4-benzylidenephenylthio)phenyldiphenylphosphonium, diphenylbenzylidenemethylhydrazine, 4-hydroxyphenylmethylbenzylhydrazine, 2-naphthylmethyl ( 1-ethoxycarbonyl)ethyl hydrazine, 4-hydroxyphenylmethylbenzhydrylmethylhydrazine, phenyl[4-(4-biphenylthio)phenyl]4-biphenyl fluorene, phenyl [4-(4-Biphenylthio)phenyl]3-biphenyl fluorene, [4-(4-ethylphenylthio)phenyl]diphenyl fluorene, octadecylmethyl benzoyl Base, diphenylanthracene, di-p-tolylhydrazine, double (4-ten Phenyl, bis(4-methoxyphenyl)fluorene, (4-octyloxyphenyl)phenylhydrazine, bis(4-decyloxy)phenylhydrazine, 4-(2-hydroxyl-10- Tetraalkoxy)phenylphenylhydrazine, 4-isopropylphenyl(p-methylphenyl)anthracene, or 4-isobutyl Phenylphenyl (p-tolyl) oxime or the like.

Among the cerium ions in the compound represented by the above formula (c1), preferred cerium ions include cerium ions represented by the following formula (c19).

In the above formula (c19), R ^8c each independently represents a group selected from a hydrogen atom, an alkyl group, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an alkylcarbonyloxy group, an alkoxycarbonyl group, a halogen atom, and a substituent. A group in which an aryl group or an arylcarbonyl group is grouped. X ^2c represents the same meaning as X ^2c in the above formula (c1).

Specific examples of the ruthenium ion represented by the above formula (c19) include 4-(phenylthio)phenyldiphenylphosphonium and 4-(4-benzylidene-2-chlorophenylthio)phenyl bis ( 4-fluorophenyl)anthracene, 4-(4-benzylidenephenylthio)phenyldiphenylanthracene, phenyl[4-(4-biphenylthio)phenyl]4-biphenylhydrazine Phenyl [4-(4-biphenylthio)phenyl]3-biphenyl fluorene, [4-(4-ethylsulfonylphenyl)phenyl]diphenyl fluorene, diphenyl [4- (p-bitriphenylthio)phenyl]diphenylphosphonium.

In the fluorinated alkyl fluorophosphate anion represented by the above formula (c17), R ^3c represents an alkyl group substituted by a fluorine atom, preferably a carbon number of 1 to 8, more preferably a carbon number of 1 to 4. Specific examples of the alkyl group include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl and octyl; isopropyl, isobutyl, sec-butyl, tert-butyl, etc. a branched alkyl group; and a cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group or a cyclohexyl group; and the ratio of the hydrogen atom of the alkyl group to the fluorine atom is usually 80 mol% or more, preferably 90% or more, and more preferably 100% by mole. In the case where the substitution ratio of the fluorine atom is less than 80 mol%, the acid strength of the fluorinated alkyl fluoride fluorophosphate represented by the above formula (c1) is lowered.

Particularly preferred R ^{3c is a} linear or branched perfluoroalkyl group having a carbon number of 1 to 4 and a fluorine atom substitution ratio of 100 mol %, and specific examples thereof include CF ₃ , CF ₃ CF ₂ , (CF). ₃ ) ₂ CF, CF ₃ CF ₂ CF ₂ , CF ₃ CF ₂ CF ₂ CF ₂ , (CF ₃ ) ₂ CFCF ₂ , CF ₃ CF ₂ (CF ₃ ) CF, (CF ₃ ) ₃ C. The number j of R ^3c is an integer of 1 to 5, preferably 2 to 4, and particularly preferably 2 or 3.

Specific examples of the preferred fluorinated alkylfluorophosphate anion include [(CF ₃ CF ₂ ) ₂ PF ₄ ] ^- , [(CF ₃ CF ₂ ) ₃ PF ₃ ] ^- , [((CF ₃ ) ₂ CF) ₂ PF ₄ ] ^- , [((CF ₃ ) ₂ CF) ₃ PF ₃ ] ^- , [(CF ₃ CF ₂ CF ₂ ) ₂ PF ₄ ] ^- , [(CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ] ^- , [((CF ₃ ) ₂ CFCF ₂ ) ₂ PF ₄ ] ^- , [((CF ₃ ) ₂ CFCF ₂ ) ₃ PF ₃ ] ^- , [(CF ₃ CF ₂ CF ₂ CF ₂ ) ₂ PF ₄ ] ^- , Or [(CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ] ^- , among these, particularly preferably [(CF ₃ CF ₂ ) ₃ PF ₃ ] ^- , [(CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ] ^- , [((CF ₃ ) ₂ CF) ₃ PF ₃ ] ^- , [((CF ₃ ) ₂ CF) ₂ PF ₄ ] ^- , [((CF ₃ ) ₂ CFCF ₂ ) ₃ PF ₃ ] ^- , or [ ((CF ₃ ) ₂ CFCF ₂ ) ₂ PF ₄ ] ^- .

Preferred examples of the borate anion represented by the above formula (c18) include quinone (pentafluorophenyl) borate ([B(C ₆ F ₅ ) ₄ ] ^- ), 肆[(trifluoromethyl)benzene. Boronate ([B(C ₆ H ₄ CF ₃ ) ₄ ] ^- ), difluorobis(pentafluorophenyl)borate ([(C ₆ F ₅ ) ₂ BF ₂ ] ^- ), trifluoro (five Fluorophenyl)borate ([(C ₆ F ₅ )BF ₃ ] ^- ), fluorenyl (difluorophenyl) borate ([B(C ₆ H ₃ F ₂ ) ₄ ] ^- )). Among them, particularly preferred is quinone (pentafluorophenyl) borate ([B(C ₆ F ₅ ) ₄ ] ^- ).

The second aspect of the component (C) includes 2,4-bis(trichloromethyl)-6-piperidin-1,3,5-triazine and 2,4-bis(trichloromethyl). -6-[2-(2-furyl)vinyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methyl-2-furyl)ethene Base]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-ethyl-2-furyl)vinyl]-s-triazine, 2,4-double (Trichloromethyl)-6-[2-(5-propyl-2-furyl)vinyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-( 3,5-Dimethoxyphenyl)vinyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,5-diethoxyphenyl)ethene Base]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,5-dipropoxyphenyl)vinyl]-s-triazine, 2,4- Bis(trichloromethyl)-6-[2-(3-methoxy-5-ethoxyphenyl)vinyl]-s-triazine, 2,4-bis(trichloromethyl)-6 -[2-(3-methoxy-5-propoxyphenyl)vinyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4- Methylenedioxyphenyl)vinyl]-s-triazine, 2,4-bis(trichloromethyl)-6-(3,4-methylenedioxyphenyl)-s-three Pyrazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)phenyl-s-triazine, 2,4-bis-trichloromethyl-6-(2- Bromo-4-methoxy)phenyl-s- Oxazine, 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)styrylphenyl-s-triazine, 2,4-bis-trichloromethyl-6- (3-Bromo-4-methoxy)styrylphenyl-s-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3, 5-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-[2-(2-furyl)ethylene 4,6-bis(trichloromethyl)-1,3,5-triazine, 2-[2-(5-methyl-2-furyl)vinyl]-4,6-bis ( Trichloromethyl)-1,3,5-triazine, 2-[2-(3,5-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-1, 3,5-triazine, 2-[2-(3,4-di Methoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4-methylenedioxyphenyl)-4, 6-bis(trichloromethyl)-1,3,5-triazine, 1,3-(dibromopropyl)-1,3,5-triazine, ginseng (2,3-dibromopropyl) The halogen-containing triazine compound, and a halogen-containing triazine compound represented by the following formula (c3), such as a triazine compound and a ginseng (2,3-dibromopropyl) trimer isocyanate.

In the above formula (c3), R ^9c , R ^10c and R ^11c each independently represent a halogenated alkyl group.

Further, in the third aspect of the component (C), α-(p-toluenesulfonyloxyimido)-phenylacetonitrile or α-(phenylsulfonyloxyimino)-2,4 may be mentioned. -dichlorophenylacetonitrile, α-(phenylsulfonyloxyimino)-2,6-dichlorophenylacetonitrile, α-(2-chlorophenylsulfonyloxyimino)-4-methoxy Phenyl phenyl acetonitrile, α-(ethylsulfonyloxyimino)-1-cyclopentenylacetonitrile, and a compound represented by the following formula (c4) containing an oxime sulfonate group.

In the above formula (c4), R ^12c represents a monovalent, divalent or trivalent organic group, R ^13c represents a substituted or unsubstituted saturated hydrocarbon group, an unsaturated hydrocarbon group or an aromatic compound group, and n represents a parenthesis. The number of repeating units constructed.

In the above formula (c4), the aromatic compound group is a group which represents a compound which exhibits physical/chemical properties peculiar to the aromatic compound, and examples thereof include an aryl group such as a phenyl group or a naphthyl group, or a furyl group or a thienyl group. Heteroaryl. These may have one or more appropriate substituents on the ring, such as a halogen atom, an alkyl group, an alkoxy group, a nitro group or the like. Further, R ^{13c is} particularly preferably an alkyl group having 1 to 6 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group and a butyl group. In particular, a compound in which R ^12c is an aromatic compound group and R ^13c is an alkyl group having 1 to 4 carbon atoms is preferred.

The acid generator represented by the above formula (c4), when n=1, R ^12c is any one of a phenyl group, a methylphenyl group and a methoxyphenyl group, and R ^13c is a methyl group, specifically Listed α-(methylsulfonyloxyimino)-1-phenylacetonitrile, α-(methylsulfonyloxyimino)-1-(p-methylphenyl)acetonitrile, α-( Methylsulfonyloxyimino)-1-(p-methoxyphenyl)acetonitrile, [2-(propylsulfonyloxyimino)-2,3-dihydroxythiophene-3-arylene Base] (o-tolyl) acetonitrile and the like. When n = 2, the photoacid generator represented by the above formula (c4), specifically, a photoacid generator represented by the following formula.

Further, the fourth aspect of the component (C) is exemplified by a phosphonium salt having a naphthalene ring in the cation portion. The phrase "having a naphthalene ring" means having a structure derived from naphthalene, and means a structure of at least two rings and maintaining the aromaticity. The naphthalene ring may have a substituent such as a linear or branched alkyl group having 1 to 6 carbon atoms, a hydroxyl group, or a linear or branched alkoxy group having 1 to 6 carbon atoms. The structure derived from the naphthalene ring may be a monovalent group (free valence of 1) or a divalent group (free valence of 2) or more, preferably a monovalent group (except that at this time, it is removed) The portion bonded to the above substituent to calculate the free atomic valence). The number of naphthalene rings is preferably from 1 to 3.

The cation portion has a cation portion of a sulfonium salt of a naphthalene ring, and preferably has a structure represented by the following formula (c5).

In the above formula (c5), at least one of R ^14c , R ^15c and R ^16c represents a group represented by the following formula (c6), and the remainder represents a linear or branched alkyl group having 1 to 6 carbon atoms. A phenyl group having a substituent, a hydroxyl group, or a linear or branched alkoxy group having 1 to 6 carbon atoms. Or one of R ^14c , R ^15c and R ^16c is a group represented by the following formula (c6), and the other two are each independently a linear or branched alkyl group having 1 to 6 carbon atoms; The ends can also be bonded to form a ring shape.

In the above formula (c6), R ^17c and R ^18c each independently represent a hydroxyl group, a linear or branched alkoxy group having 1 to 6 carbon atoms, or a linear or branched alkane having 1 to 6 carbon atoms. And R ^19c represents a single bond or a linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent. l and m each independently represent an integer of 0 to 2, and l+m is 3 or less. However, there are a plurality of cases in which R ^17c exists, and they may be identical to each other or different. Further, there are a plurality of cases in which R ^18c exists, and they may be the same or different from each other.

Among the above R ^14c , R ^15c and R ^16c , the number of the groups represented by the above formula (c6) is preferably one from the viewpoint of the stability of the compound, and the remainder is a linear or branched carbon number of 1 to 6. The alkyl group may be bonded to the end to form a ring. In this case, the above two alkylene groups contain a sulfur atom to form a 3 to 9 member ring. The number of atoms (including sulfur atoms) constituting the ring is preferably 5 to 6.

Further, the substituent which the above-mentioned alkylene group may have may be an oxygen atom (in this case, a carbonyl group is formed together with a carbon atom constituting an alkylene group), a hydroxyl group or the like.

Further, the phenyl group may have a substituent, and examples thereof include a hydroxyl group, a linear or branched alkoxy group having 1 to 6 carbon atoms, and a linear or branched alkyl group having 1 to 6 carbon atoms.

The cation portion of the above-mentioned formula (c7) or (c8) is preferable, and the structure represented by the following formula (c8) is particularly preferable.

The cation portion may be an onium salt or a phosphonium salt. From the viewpoint of acid production efficiency and the like, a phosphonium salt is preferred.

Therefore, as the anion portion having a sulfonium salt of a naphthalene ring in the cation portion, an anion capable of forming a sulfonium salt is preferred.

A part or all of the anion moiety hydrogen atom of the acid generator is fluorinated fluoroalkylsulfonate ion or arylsulfonate ion.

The alkyl group in the fluoroalkylsulfonic acid ion may be a linear chain, a branched chain or a ring having a carbon number of 1 to 20, and preferably has a carbon number of 1 in terms of a large volume of the acid produced and a diffusion distance thereof. ~10. In particular, branches or rings are preferred because of their short diffusion distance. Further, in terms of inexpensive synthesis, a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group or the like is preferable.

The aryl group in the arylsulfonic acid ion is an aryl group having 6 to 20 carbon atoms, and examples thereof include a phenyl group and a naphthyl group which may be substituted or unsubstituted with an alkyl group or a halogen atom. In particular, in the case of inexpensive synthesis, an aryl group having 6 to 10 carbon atoms is preferred. Specific examples of preferred examples include a phenyl group, a tolsulfonyl group, an ethylphenyl group, a naphthyl group, and a methylnaphthyl group.

In the above fluoroalkylsulfonate ion or arylsulfonate ion, a fluorination ratio when a part or all of a hydrogen atom is fluorinated is preferably 10 to 100%, more preferably 50 to 100%, particularly a hydrogen atom. All of them substituted by fluorine atoms are preferred because the strength of the acid is increased. Specific examples thereof include trifluoromethanesulfonate, perfluorobutanesulfonate, perfluorooctanesulfonate, and perfluorobenzenesulfonate.

Among these, the preferred anion moiety is represented by the following formula (c9).

R ^20c SO ₃ ^- (c9)

In the above formula (c9), R ^20c is a group represented by the following formulas (c10) and (c11) or a group represented by the following formula (c12).

In the above formula (c10), x represents an integer of 1 to 4. Further, in the above formula (c11), R ^21c represents a hydrogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 6 carbon atoms, or a linear or branched alkoxy group having 1 to 6 carbon atoms. , y represents an integer from 1 to 3. Among these, from the viewpoint of safety, trifluoromethanesulfonate or perfluorobutanesulfonate is preferred.

Further, the anion portion may be one containing nitrogen represented by the following formulas (c13) and (c14).

In the above formulae (c13) and (c14), X ^c represents a linear or branched alkyl group in which at least one hydrogen atom is substituted by a fluorine atom, and the alkyl group has a carbon number of 2 to 6, preferably 3~5, the best is carbon number 3. Further, Y ^c and Z ^c each independently represent a linear or branched alkyl group in which at least one hydrogen atom is replaced by a fluorine atom, and the alkyl group has a carbon number of 1 to 10, preferably 1 to 7, more preferably It is 1~3.

The smaller the carbon number of the alkyl group of X ^c or the carbon number of the alkyl group of Y ^c and Z ^c , the better the solubility in an organic solvent, which is preferable.

Further, in the alkyl group of X ^c or the alkyl group of Y ^c or Z ^c , the larger the number of hydrogen atoms substituted by fluorine atoms, the stronger the strength of the acid, which is preferable. The proportion of the fluorine atom in the alkyl group or the alkyl group, that is, the fluorination rate, is preferably 70 to 100%, more preferably 90 to 100%, and most preferably the entire hydrogen atom is replaced by a fluorine atom. An alkyl or perfluoroalkyl group.

The cation portion has a naphthalene ring and is preferably listed. The compounds represented by the following formulas (c15) and (c16) are given.

Further, the fifth aspect of the component (C) includes bis(p-toluenesulfonyl)diazomethane, bis(1,1-dimethylethylsulfonyl)diazomethane, and bis (ring). Hexylsulfonyl) diazomethanediazomethane such as diazomethane, bis(2,4-dimethylphenylsulfonyl)diazomethane; 2-nitrobenzyl p-toluenesulfonate, 2,6-dinitrobenzyl p-toluenesulfonate, nitrobenzyl p-toluenesulfonate, dinitrobenzyl tosylate, nitrobenzyl sulfonate, nitrobenzyl carbonate, dinitrobenzyl carbonate a nitrobenzyl derivative of an ester or the like; pyrogallol trifluoromethanesulfonate, pyrogallol trimethylsulfonate, benzyl tosylate, benzyl sulfonate, N-methylsulfonyloxyarene Sulphur of imine, N-trichloromethylsulfonyloxysuccinimide, N-phenylsulfonyloxymaleimide, N-methylsulfonyloxyphthalimide, etc. Acid esters; trifluoromethanesulfonates such as N-hydroxyphthalic imine, N-hydroxynaphthalene imine, etc.; diphenylphosphonium hexafluorophosphate, (4-methoxybenzene) Phenyltrifluoromethanesulfonate, bis(p-tert-butylbenzene (錪)trifluoromethanesulfonate, triphenylsulfonium hexafluorophosphate, (4-methoxyphenyl)diphenylphosphonium trifluoromethanesulfonate, (p-tert-butylphenyl) a sulfonium salt such as phenylsulfonium trifluoromethanesulfonate; a benzoin tosylate such as benzoin tosylate or α-methylbenzoin tosylate; Anthracene salt, triphenylsulfonium salt, phenyldiazonium salt, benzyl carbonate, and the like.

In the positive photosensitive resin composition of the present invention, the content of the component (C) is not particularly limited as long as it does not inhibit the object of the present invention, and is preferably 0.1 to 15 with respect to 100 parts by mass of the component (A). The mass part is more preferably 1 to 10 parts by mass.

[Nitrogen-containing organic compound (D) containing a tertiary aliphatic amine]

The positive photosensitive resin composition of the present invention may further contain the component (D). Thereby, the shape of the resist pattern is likely to be good, and for example, it is easy to obtain a resist pattern having a high verticality of the side wall and excellent squareness. Although the reason why this effect can be obtained is not clear, it is estimated that the diffusion of the acid generated by the component (C) can be effectively suppressed in the tertiary aliphatic amine uniformly dispersed resist film. Moreover, by containing the component (D), it is also easy to improve the stability of the positive photosensitive resin composition during storage and the like. The component (D) may be used singly or in combination of two or more.

The tertiary aliphatic amine has been proposed in a wide variety of ways, and any known one may be used. For example, an amine in which all three hydrogen atoms of ammonia NH ₃ are replaced by an alkyl group having 12 or less carbon atoms or a hydroxyalkyl group (for example) may be mentioned. Trialkylamine or tri(alkanol)amine).

Specific examples of the trialkylamine include, for example, trimethylamine and triethylamine. Amine, tri-n-propylamine, tri-n-butylamine, tri-n-hexylamine, tri-n-pentylamine, tri-n-heptylamine, tri-n-octylamine, three -n-decylamine, tri-n-decylamine, tri-n-dodecylamine, and the like.

Specific examples of the tri(alkanol)amine include triethanolamine, triisopropanolamine, and tri-n-octanolamine.

The tertiary aliphatic amine may be used singly or in combination of two or more.

In the component (D), the ratio of the tertiary aliphatic amine is preferably from 10 to 100% by mass, more preferably from 50 to 100% by mass, most preferably 100% by mass, in order to obtain the effect of the present invention.

In the present invention, the component (D) is within the range not detracting from the effects of the present invention. A nitrogen-containing organic compound other than a tertiary aliphatic amine may also be contained.

The nitrogen-containing organic compound other than the tertiary aliphatic amine is not particularly limited, and any one of them may be used arbitrarily. Specific examples thereof include an aliphatic amine other than a cyclic amine and a tertiary aliphatic amine.

Here, in the present invention, the "aliphatic amine" means a structure in which at least one of the three hydrogen atoms of ammonia NH ₃ is substituted with a monovalent aliphatic group, and has no chain structure in the molecule. amine. It is preferred that the aliphatic group has a carbon number of from 1 to 12.

"Cyclic amine" means an amine having a ring structure in a molecule, and the ring structure may be either aliphatic or aromatic.

The cyclic amine may, for example, be a heterocyclic compound containing a nitrogen atom as a hetero atom. The heterocyclic compound, which can be monocyclic (fat) The family of monocyclic amines can also be polycyclic (aliphatic polycyclic amines).

The aliphatic monocyclic amine is specifically, for example, piperidine or piperazine.

The aliphatic polycyclic amine is preferably a carbon number of 6 to 10, and specific examples thereof include 1,5-diazabicyclo[4.3.0]-5-nonene and 1,8-diaza Bicyclo [5.4.0]-7-undecene, hexamethylenetetramine, 1,4-diazabicyclo[2.2.2]octane, and the like.

The aliphatic amine other than the tertiary aliphatic amine may, for example, be an amine in which one hydrogen atom of ammonia NH ₃ is substituted with an alkyl group having at least 12 carbon atoms or a hydroxyalkyl group (monoalkylamine or monoalcohol). An amine); an amine (dialkylamine or di(alkyl alcohol)amine) in which two hydrogen atoms of ammonia NH ₃ are substituted with an alkyl group having 12 or less carbon atoms or a hydroxyalkyl group. Specific examples of the monoalkylamine include, for example, n-hexylamine, n-heptylamine, n-octylamine, n-decylamine, n-decylamine, and the like.

Specific examples of the dialkylamine include diethylamine, di-n-propylamine, di-n-heptylamine, di-n-octylamine, dicyclohexylamine, and the like.

Specific examples of the di(alkyl alcohol) amine include diethanolamine, diisopropanolamine, and di-n-octanolamine.

These may be used alone or in combination of two or more.

In the positive photosensitive resin composition of the present invention, the content of the component (D) is easily obtained by adding the component (D), and is preferably 0.005 to 5.0 with respect to 100 parts by mass of the component (A). The mass fraction is more preferably 0.01 to 0.3 parts by mass, and more preferably 0.015 to 0.2 parts by mass.

[Organic Solvent (S)]

The positive photosensitive resin composition of the present invention may further contain an organic solvent (S). The positive photosensitive resin composition contains an organic solvent (S), and the coating property of the positive photosensitive resin composition or the positive photosensitive resin layer formed using the positive photosensitive resin composition The adjustment of the film thickness is easy. The (S) component may be used alone or in combination of two or more.

Specific examples of the component (S) include ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, and 2-heptanone; ethylene glycol, ethylene glycol monoacetate, and Ethylene glycol, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, dipropylene glycol, and dipropylene glycol monoacetate, and monomethyl ether, monoethyl ether, monopropyl ether Polyols such as monobutyl ether or monophenyl ether (for example, propylene glycol monomethyl ether acetate) and derivatives thereof; cyclic ethers such as dioxane; ethyl formate, methyl lactate, Ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, methyl acetate, ethyl acetate, ethyl pyruvate, ethyl ethoxyacetate, methoxypropionic acid Methyl ester, ethyl ethoxypropionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, 2-hydroxy-3-methylbutyric acid An ester such as a methyl ester, 3-methoxybutyl acetate or 3-methyl-3-methoxybutyl acetate; an aromatic hydrocarbon such as toluene or xylene; or the like.

In the positive photosensitive resin composition of the present invention, the content of the organic solvent (S) is preferably from 50 to 3,000 parts by mass, more preferably from 100 to 2,000 parts by mass, per 100 parts by mass of the component (A). When the content is within the above range, the coating property of the positive photosensitive resin composition is likely to be improved, and the film thickness of the positive photosensitive resin composition layer formed using the positive photosensitive resin composition is adjusted. easily.

[Other ingredients]

The positive photosensitive resin composition of the present invention may further contain a polyvinyl resin in order to improve the plasticity of the formed film. Specific examples of the polyvinyl resin include polyvinyl chloride, polystyrene, polyhydroxystyrene, polyvinyl acetate, polyvinylbenzoic acid, polyvinyl methyl ether, polyvinyl ethyl ether, and polyethylene. An alcohol, a polyvinylpyrrolidone, a polyvinyl phenol, a copolymer of these, and the like. The polyvinyl resin is preferably a polyvinyl methyl ether from the viewpoint of a low glass transition temperature.

The positive photosensitive resin composition of the present invention may further contain a secondary auxiliary agent in order to improve the adhesion to the support.

The positive photosensitive resin composition of the present invention may further contain a surfactant in order to improve coatability, defoaming property, flatness, and the like. Specific examples of the surfactant include BM-1000, BM-1100 (both manufactured by BM Chemie Co., Ltd.), Megafac F142D, Megafac F172, Megafac F173, and Megafac F183 (all manufactured by Dainippon Ink and Chemicals Co., Ltd.), and Fluorad FC. -135, Fluorad FC-170C, Fluorad FC-430, Fluorad FC-431 (both Sumitomo 3M), Surflon S-112, Surflon S-113, Surflon S-131, Surflon S-141, Surflon S-145 (all are manufactured by Asahi Glass Co., Ltd.), SH-28PA, SH-190, SH-193, SZ-6032, SF-8428 (all manufactured by Toray Silicone Co., Ltd.), etc., but are not limited thereto. Wait.

The positive photosensitive resin composition of the present invention may further contain an acid or an acid anhydride in order to finely adjust the solubility of the developer.

Specific examples of the acid and the acid anhydride include monocarboxylic acids such as acetic acid, propionic acid, n-butyric acid, isobutyric acid, n-valeric acid, isovaleric acid, benzoic acid, and cinnamic acid; and lactic acid and 2-hydroxybutyric acid. , 3-hydroxybutyric acid, salicylic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 2-hydroxycinnamic acid, 3-hydroxycinnamic acid, 4-hydroxycinnamic acid, 5-hydroxyisophthalic acid, clove Hydroxy monocarboxylic acids such as acid; oxalic acid, succinic acid, glutaric acid, adipic acid, maleic acid, itaconic acid, hexahydrophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, 1 , 2-cyclohexanedicarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, butanetetracarboxylic acid, pyromellitic acid, trimellitic acid, cyclopentane tetracarboxylic acid, butane tetracarboxylic acid Polycarboxylic acids such as acid, 1,2,5,8-naphthalenetetracarboxylic acid; itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarballylic acid anhydride, Malay Anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, himic anhydride, 1,2,3,4-butanetetracarboxylic anhydride, cyclopentane tetracarboxylic dianhydride , phthalic anhydride, trimellitic anhydride Pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bis trimellitic anhydride, trimellitic anhydride triglyceride, etc. anhydride.

<Method for Producing Positive Photosensitive Resin Composition for Microlens Pattern Production>

The positive photosensitive resin composition for producing a microlens pattern of the present invention can be prepared by mixing and stirring the above components in a usual manner, and a dissolver, a homogenizer, or the like can be used as needed. A disperser such as a roll mill is dispersed and mixed. Further, after mixing, it may be further filtered using a mesh, a membrane filter or the like.

<Method of Manufacturing Microlens Pattern>

The method for producing a microlens pattern according to the present invention includes the step of forming a positive photosensitive resin composition layer forming a positive photosensitive resin composition layer by using the positive photosensitive resin composition of the present invention, An exposure step of selectively exposing the positive photosensitive resin composition layer, a development step of developing the exposed positive photosensitive resin composition layer after exposure, and a positive photosensitive resin composition layer after development A heating step in which heating is performed.

[Positive Photosensitive Resin Composition Layer Forming Step]

In the positive photosensitive resin composition layer forming step, the positive photosensitive resin composition layer of the present invention is used to form a positive photosensitive resin composition layer. The positive photosensitive resin composition layer is preferably formed on a substrate. The substrate may be exemplified by a lens material layer to be described later.

The method of forming the positive photosensitive resin composition layer is not particularly limited, and a conventionally known method can be used. When the positive photosensitive resin composition is a solid or a high-viscosity gel, for example, after a predetermined amount of the positive photosensitive resin composition is supplied onto a substrate, the positive photosensitive resin composition is appropriately heated and simultaneously performed. The method of pressing forms a positive photosensitive resin composition layer. When the positive photosensitive resin composition is a liquid (for example, when the positive photosensitive resin composition contains an organic solvent (S)), for example, a roll coater, a reverse roll coater, a coating bar, and a slit are used. Contact transfer type coating device such as coater, rotator (rotary coating device), shower curtain A non-contact type coating apparatus such as a curtain flow coater is formed by applying a positive photosensitive resin composition to a substrate to have a desired film thickness, and forming a coating film, which is suitable for heat treatment ( The pre-baked (PAB: post applied bake) treatment removes the organic solvent in the coating film to form a positive photosensitive resin composition layer.

The conditions of the heat treatment differ depending on the type of each component in the composition, the blending ratio, the coating film thickness, and the like, but the heating temperature is, for example, 60 to 150 ° C (preferably 70 to 140 ° C), and the heating time is, for example, 0.5~60 minutes (preferably 1~50 minutes).

The film thickness of the positive photosensitive resin composition layer is preferably in the range of 100 nm to 4.0 μm, more preferably 400 nm to 2.0 μm.

[Exposure step]

In the exposure step, the positive photosensitive resin composition layer is selectively exposed. Selective exposure can be performed, for example, via a desired mask pattern. The wavelength used for the exposure is not particularly limited, and a KrF excimer laser, an ArF excimer laser, an F ₂ excimer laser, an EUV (very ultraviolet ray), a VUV (vacuum ultraviolet ray), or an EB (electron line) can be used. , X-ray, soft X-ray and other radiation. The positive photosensitive resin composition of the present invention is particularly useful for KrF excimer lasers.

After the exposure, PEB treatment (heat treatment after exposure) is suitably carried out. The conditions for the PEB treatment vary depending on the type of each component in the composition, the blending ratio, the coating film thickness, and the like, and the heating temperature is, for example, 60 to 150 ° C (preferably 70 to 140 ° C), and the heating time is, for example, 0.5 to 60. Minutes (preferably 1~50) Minutes).

[Development Step]

In the developing step, the exposed positive photosensitive resin composition layer after exposure is developed. Thereby, the unnecessary portion is dissolved and removed.

As the developer, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, Triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo[5.4. An aqueous solution of a base such as 7-undecene or 1,5-diazabicyclo[4.3.0]-5-nonane. Further, an aqueous solution in which an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant is added to the aqueous solution of the above-mentioned alkali can also be used as a developing solution. The developer is preferably an aqueous solution of 0.1 to 10% by mass of tetramethylammonium hydroxide.

The development time varies depending on the composition of the positive photosensitive resin composition of the present invention or the film thickness of the positive photosensitive resin composition layer, and is usually from 1 to 30 minutes. The developing method may be any one of a liquid-filling method, a dipping method, a stirring method, a spray developing method, and the like.

After development, it is suitably washed with running water for 30 to 90 seconds, and dried using an air gun or an oven.

[heating step]

In the heating step, the developed positive photosensitive resin composition layer after development is heated. Thereby, the positive photosensitive resin composition layer is produced Thermal deformation, forming a microlens pattern, preferably a convex microlens pattern.

The heating conditions vary depending on the type of each component in the composition, the blending ratio, the coating film thickness, and the like. For example, the heating temperature is 130 to 170 ° C (preferably 140 to 160 ° C), and the heating time is, for example, 1 to 30 minutes. (preferably 3 to 10 minutes) or so.

<Method of Manufacturing Microlens>

The method for producing a microlens pattern according to the present invention comprises the step of: positive-type photosensitive layer in which a positive photosensitive resin composition layer is laminated on a lens material layer using the positive photosensitive resin composition of the present invention. a resin composition layer laminating step, an exposure step of selectively exposing the positive photosensitive resin composition layer, and a developing step of developing the exposed positive photosensitive resin composition layer after exposure, and the above-described positive development after development The photosensitive resin composition layer is heated to form a mask layer forming step having a mask layer of a microlens pattern, dry etching the lens material layer and the mask layer, and transferring the shape of the microlens pattern to The shape transfer step of the above lens material layer.

[Positive Photosensitive Resin Composition Layer Lamination Step]

In the positive photosensitive resin composition layer laminating step, the positive photosensitive resin composition layer of the present invention is used to laminate a positive photosensitive resin composition layer on the lens material layer. The lens material layer can be used in a conventionally known substrate such as a germanium wafer on which an image element is formed, and only a transparent planarizing film or an antireflection film and a transparent planarizing film are provided, and the transparent planarizing film is provided. The layer of lens material on.

The positive photosensitive resin composition layer lamination step can be carried out in the same manner as the positive photosensitive resin composition layer forming step in the above-described manufacturing method of the microlens pattern, except that the lens material layer as the substrate is used.

[Exposure step]

In the exposure step, the positive photosensitive resin composition layer is selectively exposed. The exposure step is the same as the exposure step in the above-described manufacturing method of the microlens pattern.

[Development Step]

In the developing step, the exposed positive photosensitive resin composition layer after exposure is developed. The developing step is the same as the developing step in the above-described manufacturing method of the microlens pattern.

[Mask layer forming step]

In the mask layer forming step, the developed positive photosensitive resin composition layer after development is heated to form a mask layer having a microlens pattern. In the mask layer forming step, the heating of the positive photosensitive resin composition layer after development can be performed in the same manner as the heating step in the above-described manufacturing method of the microlens pattern. In the mask layer forming step, the microlens pattern of the mask layer formed corresponds to the microlens pattern obtained by the above-described manufacturing method of the microlens pattern.

[Shape Transfer Step]

In the shape transfer step, the lens material layer and the mask layer are dry-etched, and the shape of the microlens pattern is transferred to the lens material layer. Thereby, the microlens can be obtained from the above lens material layer.

The dry etching is not particularly limited, and is, for example, dry etching by plasma (oxygen, argon, CF ₄ or the like), corona discharge, or the like.

[Examples]

Hereinafter, the present invention will be described in detail by way of examples, but the invention is not limited thereto.

[Examples 1 to 7 and Comparative Examples 1 to 3]

The components (A) to (D) shown in Table 1 were uniformly dissolved in an organic solvent (S) to prepare a positive photosensitive resin composition. The numerical values in parentheses in Table 1 indicate the amount of each component (unit: parts by mass).

In the following various formulae showing A-1 to A-4, the characters (x, y, and z) attached to the respective repeating units are ratios of the respective repeating units of the total repeating unit contained in the resin ( Moer%).

A-1: a resin represented by the following formula (mass average molecular weight: 20000, x=70, y=30)

A-1a: Resin represented by the following formula (mass average molecular weight 7000, x=70, y=30)

A-2: a resin represented by the following formula (mass average molecular weight: 8,000, x=75, y=25)

A-3: Resin represented by the following formula (mass average molecular weight: 20000, x=70, y=30)

A-4: Resin represented by the following formula (comparative example, mass average score Sub-quantity 10000, x=65, y=25, z=10)

B-1: a compound represented by the following formula

C-1: a compound represented by the following formula

C-2: a compound represented by the following formula

D-1: triethylamine

D-2: triethanolamine

S-1: mixed solvent of propylene glycol monomethyl ether acetate and ethyl lactate (mass ratio: 6/4)

<evaluation> [Resistance pattern shape (evaluation of bounded resolution)]

On the substrate on which the antireflection film and the acrylic transparent flattening film were formed on the Si substrate, a positive photosensitive resin composition prepared in the examples or the comparative examples was applied using a spin coater to form a coating film. The coating film was pre-baked at 100 ° C for 90 seconds on the hot plate to dry the coating film to form a positive photosensitive resin composition layer having a thickness of 800 nm.

Next, a KrF excimer laser (248 nm) was selectively irradiated onto the positive photosensitive resin composition layer through a mask using a KrF exposure apparatus NSR-S203B (manufactured by Nikon, NA=0.68, S=0.75).

Then, the positive-type photosensitive resin composition layer was subjected to PEB treatment at 110 ° C for 90 seconds, and then developed at 23 ° C for 2.3 seconds with a 2.38 mass % aqueous solution of tetramethylammonium hydroxide for 60 seconds. The water was washed for 30 seconds. The pure water is dried and dried to obtain a resist pattern.

The cross section of the obtained resist pattern was observed using SEM. By varying the mask size, the critical resolution is sought and the critical resolution is evaluated according to the following criteria. The results are shown in Table 2.

◎ (very good): the critical resolution is less than 0.17μm

○ (good): The critical resolution is more than 0.17 μm and 0.18 μm or less.

△ (bad): the critical resolution is more than 0.18 μm and 0.19 μm or less

× (very bad): the limit resolution is more than 0.19μm

[Evaluation of resolution (width of white band)]

As in the above, the obtained resist pattern was observed by SEM from above. The width of the white energy band appearing around each resist pattern was measured and evaluated according to the following criteria. The results are shown in Table 2. The white band is confirmed when the size of the bottom portion is larger than the size of the top portion of the resist pattern. The width of the wide top portion and the bottom portion of the white energy band is different, indicating the degree of the tapered shape. The smaller the width of the white band, the higher the verticality of the pattern and the better.

◎ (very good): the width of the white energy band is less than 0.07μm

○ (good): the width of the white energy band is 0.07 μm or more and less than 0.075 μm.

△ (bad): the width of the white energy band is 0.075 μm or more and less than 0.08 μm.

× (very bad): the width of the white energy band is 0.08 μm or more

[Evaluation of Liquidity (Margin)]

Similarly to the above, the obtained resist pattern was subjected to post-baking treatment at a temperature of 130 to 170 ° C for 300 seconds, and the cross section of the resist pattern was observed by SEM. The lowest temperature T _{1 at} which the microlens pattern is formed by the post-baking process and the lowest temperature T _{2 in} contact with the lower portion of the adjacent microlens pattern are obtained. The difference T ₂ -T _{1 was taken} as a flow margin and evaluated based on the following criteria. The results are shown in Table 2.

◎ ◎ (very good): the flow margin is 10 ° C or more

◎ (good): the flow margin is above 7 ° C, less than 10 ° C

○ (slightly good): The flow margin is 4 ° C or more and less than 7 ° C

× (bad): the flow margin is less than 4 ° C

As is clear from Table 2, the compositions of Examples 1 to 7 containing the components (A) and (B) of the present invention have excellent resolution and a wide flow margin. On the other hand, the composition of Comparative Examples 1 to 3 which does not contain the component (A) and/or the component (B) of the present invention has a small flow margin.

Claims (9)

A positive photosensitive resin composition containing a resin (A) having an acid dissociable dissolution inhibiting group and an increase in solubility to a base by an action of an acid, and a compound having at least two ethyleneoxy groups (B) And a positive photosensitive resin composition for producing a microlens pattern of the photoacid generator (C), wherein the resin (A) contains a constituent unit (a1) derived from hydroxystyrene and derived from hydroxystyrene A resin (A1) constituting the unit (a2) in which a hydrogen atom of at least one hydroxyl group in the unit is substituted with a group containing an acid dissociable dissolution inhibiting group. The positive photosensitive resin composition of claim 1, wherein the resin (A1) has a mass average molecular weight of 5,000 to 30,000. The positive-type photosensitive resin composition of the first aspect of the invention, wherein the resin (A1) contains a constituent unit represented by the following formula (a1-1) and a constituent unit represented by the following formula (a2-1). Resin (A2), (wherein R ^a1 and R ^a3 independently represent a hydrogen atom, an alkyl group, a halogen atom, or an alkyl group substituted with a halogen atom, R ^a2 and R ^a5 independently represent an alkyl group, and R ^a4 represents an acid dissociable dissolution inhibiting group, p And r independently represents an integer from 1 to 5, and q, s, and t independently represent integers from 0 to 4, but p+q and r+s+t are independently integers from 1 to 5. The positive photosensitive resin composition of the third aspect of the invention, wherein the resin (A2) contains a constituent unit represented by the formula (a1-1) and a constituent unit represented by the following formula (a2-2) / or a resin (A3) constituting the unit represented by the following formula (a2-3), (wherein, R ^a3 , R ^a5 , r, s, and t are as defined above, and R ^a6 and R ^a7 independently represent a hydrogen atom or an alkyl group, and R ^a8 and R ^a10 independently represent an alkyl group or a cycloalkyl group, and R ^a9 represents A single bond or an alkyl group, but at least two of R ^a6 , R ^a7 , and R ^{a8 are} bonded to each other to form a ring). The positive photosensitive resin composition of the fourth aspect of the invention, wherein the resin (A3) contains a constituent unit represented by the above formula (a1-1) and a constituent unit represented by the above formula (a2-2) Resin (A4) and / Or a resin (A5) having a constituent unit represented by the above formula (a1-1) and a constituent unit represented by the above formula (a2-3). The positive photosensitive resin composition of the fifth aspect of the invention, wherein the amount of the resin (A4) is 60 to 90 mol% based on the total of the resin (A4) and the resin (A5). The positive photosensitive resin composition of claim 1, which further comprises a nitrogen-containing organic compound (D) containing a tertiary aliphatic amine. A method for producing a microlens pattern comprising the step of forming a positive photosensitive resin composition layer of a positive photosensitive resin composition layer using a positive photosensitive resin composition as in the first aspect of the patent application a forming step of exposing the positive photosensitive resin composition layer to an exposure step, a developing step of developing the exposed positive photosensitive resin composition layer after exposure, and a positive photosensitive resin after development A heating step in which the composition layer is heated. A method for producing a microlens, comprising the steps of: laminating a positive photosensitive resin composition layer onto a lens material layer using a positive photosensitive resin composition as in claim 1 of the patent application; Resin composition layer laminating step, exposing step of selectively exposing the positive photosensitive resin composition layer a developing step of developing the exposed positive photosensitive resin composition layer after exposure, and heating the developed positive photosensitive resin composition layer to form a mask having a microlens pattern mask layer a layer forming step of dry-etching the lens material layer and the mask layer, and transferring the shape of the microlens pattern to a shape transfer step of the lens material layer.