KR20160090264A - 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

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a positive-type photosensitive resin composition for the production of a micro lens pattern (Positive-type Photosensitive Resin Composition for Microlens Pattern)

The present invention relates to a positive photosensitive resin composition for producing a micro lens pattern, a method of manufacturing a micro lens pattern using the same, and a method of manufacturing a micro lens.

Conventionally, solid-state image pickup devices are used for cameras, video cameras, and the like. A CCD (charge-coupled device) image sensor or a CMOS (complementary metal-oxide semiconductor) image sensor is used for the solid-state image pickup device. The image sensor is provided with a fine condensing lens (hereinafter referred to as a microlens) for the purpose of improving the light collection efficiency.

The microlenses are formed by an etching method using, for example, a positive photosensitive resin composition. Specifically, a positive-type photosensitive resin composition layer is formed on a lens material layer using a positive-type photosensitive resin composition, and then the positive-type photosensitive resin composition layer is selectively exposed. Then, the exposed portion is removed by development, and then the positive photosensitive resin composition layer is fluidized by heat treatment to form a mask layer having a micro lens pattern. Thereafter, the microlens is obtained by dry etching the lens material layer and the mask layer, and transferring the shape of the microlens pattern to the lens material layer. Conventionally, as a positive photosensitive resin composition for forming a micro lens pattern used for forming the mask layer, for example, acrylic or novolac-based positive resist materials have been used (Patent Document 1).

Japanese Patent Laid-Open Publication No. 2013-117662

The positive photosensitive resin composition for producing a micro lens pattern as described above is required to have excellent resolution and a wide flow margin (a temperature width capable of forming a good micro lens pattern). However, Characteristics are not enough.

SUMMARY OF THE INVENTION The present invention has been made in view of such conventional circumstances, and it is an object of the present invention to provide a positive photosensitive resin composition for manufacturing a micro lens pattern having both excellent resolution and a wide flow margin, a method of manufacturing a micro lens pattern using the same, And to provide the above objects.

The inventors of the present invention have found that the above problems can be solved by combining a specific resin having an acid dissociable, dissolution inhibiting group that increases solubility in alkali by the action of an acid and a compound having at least two vinyloxy groups, It came to the following. Specifically, the present invention provides the following.

A first aspect of the present invention is a curable composition comprising a resin (A) having an acid dissociable, dissolution inhibiting group and being increased in solubility in alkali by the action of an acid, a compound (B) having at least two vinyloxy groups, a photoacid generator Wherein the resin (A) is a positive-working photosensitive resin composition comprising a structural unit (a1) derived from hydroxystyrene and a structural unit derived from a hydroxystyrene having at least one hydrogen atom of a hydroxyl group And a resin (A1) having a structural unit (a2) substituted with an acid dissociable, dissolution inhibiting group-containing group.

A second aspect of the present invention is a process for producing a positive photosensitive resin composition comprising a positive photosensitive resin composition layer forming step of forming a positive photosensitive resin composition layer by using the positive photosensitive resin composition, an exposure step of selectively exposing the positive photosensitive resin composition layer, A developing step of developing the exposed positive photosensitive resin composition layer, and a heating step of heating the positive photosensitive resin composition layer after development.

A third aspect of the present invention relates to a positive photosensitive resin composition layer-laminating process for laminating a positive-type photosensitive resin composition layer on a lens material layer using the positive-type photosensitive resin composition, and a positive-working photosensitive resin composition layer- A mask layer forming step of forming a mask layer having a microlens pattern by heating the developed positive photosensitive resin composition layer after developing the negative photoresist composition layer; And a shape transfer step of dry-etching the material layer and the mask layer, and transferring the shape of the micro lens pattern to the lens material layer.

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

≪ Positive photosensitive resin composition for producing micro lens pattern >

The positive photosensitive resin composition for producing a micro lens pattern according to the present invention comprises a resin (A) having an acid dissociable, dissolution inhibiting group and being capable of increasing solubility in alkali by the action of an acid, a compound (B) having at least two vinyloxy groups, And a photoacid generator (C), wherein the resin (A) comprises a structural unit (a1) derived from hydroxystyrene and a structural unit derived from a hydroxystyrene, wherein at least one hydrogen atom of the hydroxyl group in the structural unit derived from hydroxystyrene is acid dissociable And a resin (A1) having a constituent unit (a2) substituted with an inhibitor-containing group. This positive photosensitive resin composition is suitably used for the formation of a mask layer having a micro lens pattern in the production of a microlens by an etching method. Hereinafter, each component contained in the positive photosensitive resin composition will be described in detail.

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

The resin (A) having an acid dissociable, dissolution inhibiting group and increasing the solubility in alkali by the action of an acid is a copolymer of a structural unit (a1) derived from hydroxystyrene and a structural unit (A1) having a structural unit (a2) in which a hydrogen atom of the acid-dissociable, dissolution inhibiting group is replaced with an acid-dissociable, dissolution-inhibiting group-containing group. The resin (A) may be used alone or in combination of two or more.

When the resin (A) contains the resin (A1) having the structural unit (a1) and the structural unit (a2), the resulting positive photosensitive resin composition tends to have excellent resolution and tends to secure a wide flow margin.

As the structural unit (a1), for example, a structural unit represented by the following general formula (a1-1) can be exemplified. As the structural unit (a2), for example, a structural unit represented by the following general formula (a2-1) can be exemplified.

However,

(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, R ^a4 represents an acid dissociable dissolution inhibiting group , p and r independently represent an integer of 1 to 5, q, s and t independently represent an integer of 0 to 4, provided that p + q and r + s + t are independently an integer of 1 to 5 to be)

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 with a halogen atom. The alkyl group represented by R ^a1 and R ^a3 is an alkyl group having 1 to 5 carbon atoms and is preferably a linear or branched alkyl group and is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, Pentyl group, isopentyl group, neopentyl group and the like. The methyl group is preferable industrially. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is particularly preferable. As the alkyl group substituted with a halogen atom, a part or all of hydrogen atoms of the above-mentioned alkyl group having 1 to 5 carbon atoms is substituted with a halogen atom. In the present invention, it is preferable that all the hydrogen atoms are halogenated. The alkyl group substituted with a halogen atom is preferably a linear or branched alkyl group substituted with a halogen atom, and more preferably a fluorinated alkyl group such as a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, and a nonafluorobutyl group, Most preferred is a trifluoromethyl group (-CF ₃ ). As R ^a1 and R ^a3 , a hydrogen atom or a methyl group is preferable, and a hydrogen atom is more preferable.

Examples of the alkyl group having 1 to 5 carbon atoms for R ^a2 and R ^a5 include the same alkyl groups as R ^a1 and R ^a3 . q, s, and t are independently an integer of 0 to 4; Of these, q, s and t are preferably 0 or 1, and particularly preferably 0 in industrial terms. The substitution position of R ^a2 may be any of o-position, m-position, and p-position when q is 1, and arbitrary substitution positions may be combined when q is an integer of 2 to 4. The substitution position of R ^a5 may be any one of o-position, m-position and p-position when t is 1, and arbitrary substitution positions may be combined when t is an integer of 1 to 4. p and r each represents an integer of 1 to 5, preferably an integer of 1 to 3, and preferably 1. The substitution position of the hydroxyl group may be any of o-position, m-position and p-position when p and s are 1, but it is preferably p-position in that it is readily available and inexpensive. When p is an integer of 2 to 5 and s is an integer of 2 to 4, arbitrary substitution positions can be combined.

The acid dissociable, dissolution inhibiting group represented by R ^a4 includes a group represented by the following formula (a2-1-1), a group represented by the following formula (a2-1-2), a straight chain, branched or cyclic An alkyl group, a vinyloxyethyl group, a tetrahydropyranyl group, a tetrafuranyl group, or a trialkylsilyl group.

[Figure 2]

In the formulas (a2-1-1) and (a2-1-2), R ^a6 and R ^a7 independently represent a hydrogen atom or an alkyl group, R ^a8 and R ^a10 independently represent an alkyl group or a cycloalkyl group, R ^a9 represents a single bond or an alkylene group, provided that at least two of R ^a6 , R ^a7 and R ^a8 may be bonded to each other to form a ring.

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

Examples of the linear or branched alkyl group include a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group and neopentyl group. Examples of the cycloalkyl group include a cyclopentyl group and a cyclohexyl group. Examples of the alkylene group include a methylene group, an ethylene group, a methylmethylene group, a propylene group, an isopropylene group, and an ethylmethylene group.

Specific examples of the acid dissociable, dissolution inhibiting group represented by the formula (a2-1-1) include methoxyethyl, ethoxyethyl, n-propoxyethyl, isopropoxyethyl, n-butoxyethyl, isobutoxy Ethyl group, tert-butoxyethyl group, cyclohexyloxyethyl group, methoxypropyl group, ethoxypropyl group, 1-methoxy-1-methyl-ethyl group and 1-ethoxy-1-methylethyl group. Specific examples of the acid dissociable, dissolution inhibiting group represented by the formula (a2-1-2) include a tert-butoxycarbonyl group and a tert-butoxycarbonylmethyl group. Examples of the trialkylsilyl group include alkyl groups having 1 to 6 carbon atoms such as trimethylsilyl group and tri-tert-butyldimethylsilyl group.

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

The total proportion of the constituent units (a1) and (a2) in the resin (A1) is preferably 10 to 100 mol%, more preferably 30 to 100 mol%, relative to all the constituent units constituting the resin (A1) , More preferably 50 to 100 mol%, particularly preferably 70 to 100 mol%, most preferably 100 mol%. If the ratio is within the above range, the resulting positive-working photosensitive resin composition tends to have better resolution, more easily obtain a wider flow margin, and is well balanced with other constituent units.

The proportion of the constituent unit (a2) (that is, the protection ratio of hydroxystyrene) in the total of the constituent units (a1) and (a2) is preferably from 10 to 60 mol%, more preferably from 20 to 40 mol% . When the protective ratio of hydroxystyrene is within the above range, the resulting positive-working photosensitive resin composition tends to be more excellent in resolution and tends to have a wider flow margin.

(Other constituent units)

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

- Constituent unit (a3)

The structural unit (a3) is a structural unit derived from styrene. When the content of the constituent unit (a3) is adjusted and the content of the constituent unit (a3) is adjusted, the solubility of the resin (A1) in an alkali developing solution can be adjusted, and when the alkali solubility of the thick film There is a possibility that the shape can be further improved.

Here, the term " styrene " means a styrene which is contemplated, and hydrogen atoms at the [alpha] -position of styrene in the stucture are substituted with other substituents such as a halogen atom, an alkyl group and a halogenated alkyl group, and derivatives thereof. The term "structural unit derived from styrene" means a structural unit in which an ethylene double bond of styrene is cleaved and constituted. The styrene may be substituted with a substituent such as a lower alkyl group (for example, an alkyl group having 1 to 5 carbon atoms) of the hydrogen atom of the phenyl group.

As the structural unit (a3), a structural unit represented by the following general formula (a3-1) can be exemplified.

[Figure 3]

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

As R, the same groups as those exemplified above for R ^a1 and R ^a3 can be mentioned. As R ⁷ , the same groups as those exemplified above for R ^a2 and R ^a5 can be mentioned.

r is an integer of 0 to 3; Among them, r is preferably 0 or 1, and particularly preferably 0 in industrial terms.

The substitution position of R ⁷ may be any of o-position, m-position and p-position when r is 1, and arbitrary substitution positions may be combined when r is 2 or 3.

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

The proportion of the structural unit (a3) in the resin (A1) is preferably 0 to 90 mol%, more preferably 0 to 70 mol%, and even more preferably 0 to 50 mol%, based on the total structural units constituting the resin (A1) Mol, more preferably 0 to 30 mol%, and most preferably 0 mol%. If the ratio is within the above range, 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 all the constituent units constituting the resin (A1). When the lower limit is the above-mentioned value, the effect of having the structural unit (a3) tends to be enhanced.

- Constituent unit (a4)

The structural unit (a4) is a structural unit derived from an acrylate ester having an alcoholic hydroxyl group. By having such a structural unit (a4), the effect of the present invention may be further improved.

As the preferable structural unit (a4), a structural unit having a straight chain or cyclic alkyl group having an alcoholic hydroxyl group can be exemplified. That is, the structural unit (a4) is preferably a structural unit derived from an acrylic acid ester having an alcoholic hydroxyl group-containing chain or cyclic alkyl group.

When the constituent unit (a4) has a constituent unit derived from an acrylate ester having a cyclic alkyl group containing an alcoholic hydroxyl group (hereinafter sometimes simply referred to as "constituent unit having a hydroxyl group-containing cyclic alkyl group"), And the etching resistance may be improved.

When the constituent unit (a4) has a constituent unit derived from an acrylate ester having a straight chain alkyl group containing an alcoholic hydroxyl group (hereinafter sometimes simply referred to as "constituent unit having a hydroxyl group-containing straight chain alkyl group"), The hydrophilicity of the whole may be increased and the affinity with the developer may be increased in some cases, thereby improving the resolution.

Structural units having a hydroxyl group-containing cyclic alkyl group

Examples of the structural unit having a hydroxyl group-containing cyclic alkyl group include a structural unit in which a hydroxyl group-containing cyclic alkyl group is bonded to an ester group [-C (O) O-] of an acrylic acid ester. Here, the "hydroxyl group-containing cyclic alkyl group" is a group in which a hydroxyl group is bonded to a cyclic alkyl group.

The hydroxyl groups are preferably bonded, for example, from 1 to 3, more preferably one.

The cyclic alkyl group may be monocyclic or polycyclic, but is preferably a polycyclic group. The cyclic alkyl group preferably has 5 to 15 carbon atoms.

Specific examples of the cyclic alkyl group include the following.

Examples of the monocyclic cyclic alkyl group include groups in which one to four hydrogen atoms are removed from the cycloalkane. More specifically, examples of the monocyclic cyclic alkyl group include groups excluding one to four hydrogen atoms from a cycloalkane such as cyclopentane, cyclohexane, etc. Among them, a cyclohexyl group is preferable.

Examples of the polycyclic cyclic alkyl group include groups in which one to four hydrogen atoms have been removed from polycycloalkanes such as bicycloalkane, tricycloalkane, and tetracycloalkane. More specifically, there may be mentioned a group in which one to four hydrogen atoms are removed from a polycycloalkane such as adamantane, norbornane, isoborane, tricyclodecane or tetracyclododecane.

Such a cyclic alkyl group can be appropriately selected and used from among many proposed ones for constituting an acid dissociable dissolution inhibiting group in a resin for a photoresist composition for an ArF excimer laser process, for example. Of these, a cyclohexyl group, an adamantyl group, a norbornyl group, and a tetracyclododecanyl group are industrially easily available and preferable.

Of these monocyclic groups and polycyclic groups, cyclohexyl group and adamantyl group are preferable, and adamantyl group is particularly preferable.

As a specific example of the structural unit having a hydroxyl group-containing cyclic alkyl group, for example, a structural unit (a4-1) represented by the following general formula (a4-1) is preferable.

[Figure 4]

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

As R, the same groups as those exemplified above for R ^a1 and R ^a3 can be mentioned.

s is an integer of 1 to 3, with 1 being most preferred.

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

Structural units having a hydroxyl group-containing straight chain alkyl group

Examples of the structural unit having a hydroxyl group-containing chain alkyl group include a structural unit in which a chain hydroxyalkyl group is bonded to an ester group [-C (O) O-] of an acrylic acid ester. Here, the "chain hydroxyalkyl group" means a group formed by replacing part or all of hydrogen atoms in a chain (linear or branched) alkyl group with a hydroxyl group.

As the constituent unit having a hydroxyl group-containing chain alkyl group, a constituent unit (a4-2) represented by the following general formula (a4-2) is preferable.

[Figure 5]

Wherein R is the same as defined above, and R ⁸ is a straight-chain hydroxyalkyl group.

As R, the same groups as those exemplified above for R ^a1 and R ^a3 can be mentioned.

The hydroxyalkyl group of R ⁸ is preferably a hydroxyalkyl group having 1 to 10 carbon atoms, more preferably a hydroxyalkyl group having 2 to 8 carbon atoms, and still more preferably a linear hydroxyalkyl group having 2 to 4 carbon atoms .

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

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

The proportion of the structural unit (a4) in the resin (A1) is preferably 0 to 90 mol%, more preferably 0 to 70 mol%, and more preferably 0 to 50 mol%, relative to the total structural units constituting the resin (A1) Mol, more preferably 0 to 30 mol%, and most preferably 0 mol%. If the ratio is within the above range, 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 all the constituent units constituting the resin (A1). If the lower limit is the above-mentioned value, the effect of having the structural unit (a4) tends to be enhanced.

The resin (A1) may contain other constituent units (a5) other than the constituent units (a1) to (a4) within the range not to impair the effect of the present invention.

The constituent unit (a5) is not particularly limited as long as it is other constituent units not classified in the above-mentioned constituent units (a1) to (a4), and is preferably used for ArF excimer laser, KrF positive excimer laser (preferably KrF excimer laser) And the like, which are conventionally known, can be used.

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

In the component (A), the proportion of the resin (A1) is preferably 50 to 100% by weight, more preferably 80 to 100% by weight, and most preferably 100% by weight for the effect of the present invention.

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

[6]

( ^Wherein R ^a1 to R ^a5 and p to t are the same as above)

When the resin (A1) contains the resin (A2), the resulting positive-working photosensitive resin composition tends to have better resolution and more easily obtain a wider flow margin.

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

The ratio of the resin (A2) in the resin (A1) is preferably 50 to 100% by weight, more preferably 80 to 100% by weight, and most preferably 100% by weight for the effect of the present invention.

The resin (A2) is obtained by reacting the resin (A3) having the structural unit represented by the formula (a1-1), the structural unit represented by the following formula (a2-2) and / or the structural unit represented by the following formula (a2-3) .

[Figure 7]

( ^Wherein R ^a3 , R ^a5 to R ^a10 , r, s, and t are as defined above)

When the resin (A2) contains the resin (A3), the resulting positive-working photosensitive resin composition tends to have better resolution and is more likely to have a wider flow margin.

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

The proportion of the resin (A3) in the resin (A2) is preferably 50 to 100% by weight, more preferably 80 to 100% by weight, and most preferably 100% by weight for the effect of the present invention.

The resin (A3) is obtained by copolymerizing the structural unit represented by the formula (a1-1) and the resin (A4) having the structural unit represented by the formula (a2-2) and / or the structural unit represented by the formula (a1-1) , And a resin (A5) having a structural unit represented by the above formula (a2-3).

When the resin (A3) contains the resin (A4) and / or the resin (A5), the resulting positive-working photosensitive resin composition tends to have better resolution than that of the positive-working photosensitive resin composition.

Particularly, when the resin (A3) contains both of the resin (A4) and the resin (A5), it is preferable that both of the high resolution and the wide flow margin are easy to be achieved.

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

The total proportion of the resins (A4) and (A5) in the resin (A3) is preferably 50 to 100% by weight, more preferably 80 to 100% by weight, and most preferably 100% %to be.

The amount of the resin (A4) is preferably 60 to 90 mol%, more preferably 70 to 80 mol%, based on the total amount of the resin (A4) and the resin (A5). When the amount of the resin (A4) is within the above range, the resulting positive-working photosensitive resin composition tends to have particularly excellent resolution, and particularly a wide flow margin is liable to be secured.

The weight average molecular weight (Mw) of the resin (A1) is preferably 5000 to 30,000. The same applies to the weight average molecular weights of the resins (A2) and (A3). When the weight average molecular weight is within the above range, the resulting positive-working photosensitive resin composition tends to have good resolution, heat resistance and flowability. In the present specification, the weight average molecular weight refers to the polystyrene-reduced weight average molecular weight determined by gel permeation chromatography (GPC).

The weight average molecular weight of the resin (A4) is preferably 15,000 to 30,000, more preferably 17,000 to 25,000. If the weight average molecular weight is 15,000 or more, the resulting positive photosensitive resin composition tends to have a high flow margin because heat resistance is easily improved and the flow property is only increased. On the other hand, if the weight average molecular weight is 30,000 or less, the resulting positive-working photosensitive resin composition tends to have excellent resolution.

The weight average molecular weight of the resin (A5) is preferably 5000 to 15000, more preferably 7000 to 10000. When the weight average molecular weight is within the above range, the resulting positive-working photosensitive resin composition tends to have good heat resistance and flow properties.

In the present invention, in addition to the resin (A1), a resin which is generally used as a resin for chemically amplifying positive resist such as a PHS-based resin or an acrylic resin may be contained within the range that does not impair the effect of the present invention as the component (A) do.

The weight average molecular weight (Mw) of the resin (A) is preferably 5,000 to 30,000. When the weight average molecular weight is within the above range, the resulting positive-working photosensitive resin composition tends to have good resolution, heat resistance and flowability.

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

[Compound (B) having at least two vinyloxy groups]

The compound (B) having at least two vinyloxy 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. By containing such a compound, the obtained positive-working photosensitive resin composition tends to have excellent resolution and a wide flow margin is easily ensured. (B) may be used alone or in combination of two or more.

It is presumed that the compound (B) having at least two vinyloxy groups exerts the above effect by acting as a crosslinking agent for the component (A). That is, the compound (B) having at least two vinyloxy groups undergoes a crosslinking reaction with the component (A) by heating at the time of prebaking, and forms an alkali-insoluble resist layer on the entire surface of the substrate. Thereafter, it is presumed that the dissolution contrast is improved because the crosslinking is decomposed by the action of the acid generated from the component (B) upon exposure to change the exposed portion to alkali soluble and the unexposed portion to remain insoluble. It is also presumed that the crosslinking with the resin (A) proceeds further during the post-baking, thereby improving the flow margin.

As the compound (B) having at least two vinyloxy groups, there are many listed in JP-A-6-148889 and JP-A-6-230574, among others. Particularly, in view of the resist profile shape due to thermal crosslinking and degradability by an acid, and the contrast characteristics of the exposed portion and the unexposed portion, a part or all of the hydroxyl groups of the alcohol represented by the following general formula (f-2) A compound obtained by ether substitution of a hydrogen atom with a vinyl group is preferable.

Rb- (OH) _b (f-2)

In the formulas, Rb is a group excluding b hydrogen atoms from a linear, branched, or cyclic alkane, and may have a substituent. In the alkane, an oxygen bond (ether bond) may be present. b represents 2, 3, or 4;

Specific examples include ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,3-butanediol divinyl ether, tetramethylene glycol divinyl ether, neopentyl glycol divinyl ether, trimethylolpropane trivinyl ether, trimethylol ethane tri Vinyl ether, hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, tetraethylene glycol divinyl ether, pentaerythritol divinyl ether, pentaerythritol trivinyl ether, cyclohexanedimethanol divinyl ether, and the like. .

The compound (B) having at least two vinyloxy groups is also 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 straight chain alkylene group having 1 to 10 carbon atoms or a group represented by the following formula (f-4). R ²⁷ may have a substituent. R ²⁷ may contain an oxygen bond (ether bond) in the main chain.

[Figure 8]

In the general formula (f-4), R ²⁸ is a branched or straight chain alkylene group having 1 to 10 carbon atoms which may independently have a substituent, and the alkylene group includes an oxygen bond (ether bond) . c is independently 0 or 1;

R ²⁷ is preferably a group represented by -C ₄ H ₈ -, -C ₂ H ₄ OC ₂ H ₄ -, -C ₂ H ₄ OC ₂ H ₄ OC ₂ H ₄ - and the general formula (f-4) , The group represented by the general formula (f-4) is particularly preferable, and the group represented by the general formula (f-4) wherein R ²⁸ is an alkylene group having 1 carbon atom (that is, a methylene group) and c is 1 is preferable.

As the compound represented by the general formula (f-3), cyclohexanedimethanol divinyl ether [hereinafter abbreviated as CHDVE] is preferable.

The content of the component (B) in the positive-type photosensitive resin composition according to the present invention is preferably 0.1 to 15 parts by weight per 100 parts by weight of the component (A) from the viewpoint of improving the resolution and the flow margin of the positive- By weight, more preferably 1 to 8 parts by weight.

[Photo acid 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 upon irradiation with an actinic ray or radiation. (C) may be used alone or in combination of two or more.

As the component (C), the photoacid generators of the first to fifth embodiments described below are preferable. Preferred examples of the component (C) are described below as the first to fifth aspects.

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

[Figure 9]

In the formula (c1), X ^1c represents a sulfur atom or an iodine atom having a valence of 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 is 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, an alkenyl group having 2 to 30 carbon atoms, represents an alkynyl group, R ^1c is alkyl, hydroxy, alkoxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxy carbonyl, arylthio carbonyl, acyloxy, arylthio, alkylthio, aryl, a heterocyclic ring May be substituted with at least one member selected from the group consisting of aryloxy, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, alkyleneoxy, amino, cyano and nitro groups and halogen . The number of R ^1c is g + h (g-1) +1, and R ^1c may be the same or different from each other. In addition, two or more of R ^1c to each other directly, or _{-O-, -S-, -SO-, -SO 2} -, -NH-, -NR 2c -, -CO-, -COO-, -CONH-, An alkylene group having 1 to 3 carbon atoms, or a phenylene group to 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).

[10]

In formula (c2), X ^4c represents an alkylene group having 1 to 8 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a bicyclic compound having 8 to 20 carbon atoms, and X ^4c is an alkyl group having 1 to 8 carbon atoms , Alkoxy of 1 to 8 carbon atoms, aryl of 6 to 10 carbon atoms, each group of hydroxy, cyano and nitro, and halogen. X ^5c represents an alkylene group having 1 to 3 carbon atoms or a group represented by -O-, -S-, -SO-, -SO ₂ -, -NH-, -NR ^2c -, -CO-, -COO-, Phenylene group. h represents the number of repeating units of the structure in parentheses. h + 1 X ^4c and h X ^5c may be the same or different from each other. R ^2c has the same definition as described above.

X ^{3c -} is a counterion of onium, a fluorinated alkyl fluorophosphate anion represented by the following formula (c17) or a borate anion represented by the following formula (c18).

[Figure 11]

In the formula (c17), R ^3c represents an alkyl group in which at least 80 mol% of hydrogen atoms have been substituted with fluorine atoms. j represents the number, and is an integer of 1 to 5. j R ^3c may be the same or different from each other.

[Figure 12]

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

As the onium ion in the compound represented by the formula (c1), triphenylsulfonium, tri-p-tolylsulfonium, 4- (phenylthio) phenyldiphenylsulfonium, bis [4- (diphenylsulfonio) Phenyl] sulfide, bis {4- [bis (4-fluorophenyl) sulfonio] phenyl} Sulfide, 9-oxo-10-thia-9,10-dihydroanthracene-2 (2-chlorophenylthio) phenylbis 2-yldiphenylsulfonium, 2 - [(diphenyl) sulfonio] thioxane, 2-methyl-2- (4-tert-butylbenzoyl) phenylthio] phenyldi-p-tolylsulfonium, 4- (4- benzoylphenylthio) phenyldiphenylsulfonium, diphenylphenacathisulfonium, 4- (4-hydroxyphenylmethylphenylsulfonyl), phenyl [4- (4-biphenylsulfonyl) phenyl] Biphenylsulfonium, phenyl [4- (4-acetophenylthio) phenyl] diphenylsulfonium, phenyl [4- Iodonium, bis (4-methoxyphenyl) iodonium, bis (4-methoxyphenyl) iodonium, ) Is at least one compound selected from the group consisting of phenyl iodonium, bis (4-decyloxy) phenyl iodonium, 4- (2-hydroxytetradecyloxy) phenylphenyl iodonium, , Or 4-isobutylphenyl (p-tolyl) iodonium.

Among the onium ions in the compound represented by the formula (c1), the preferable onium ion includes a sulfonium ion represented by the following formula (c19).

[Figure 13]

In the formula (c19), each R ^8c independently represents a hydrogen atom, an alkyl, a hydroxy, an alkoxy, an alkylcarbonyl, an alkylcarbonyloxy, an alkyloxycarbonyl, a halogen atom, ≪ / RTI > X ^2c have the same meanings as X ^2c in the formula (c1).

Specific examples of the sulfonium ion represented by the formula (c19) include 4- (phenylthio) phenyldiphenylsulfonium, 4- (4-benzoyl-2-chlorophenylthio) phenylbis Phenyl [4- (4-biphenylthio) phenyl] diphenylsulfonium, phenyl [4- [4- (4-acetophenylthio) phenyl] diphenylsulfonium, diphenyl [4- (p-terphenylthio) phenyl] diphenylsulfonium.

In the fluorinated alkyl fluorophosphate anion represented by the formula (c17), R ^3c represents an alkyl group substituted with a fluorine atom, preferably 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms. Specific examples of the alkyl group include straight chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl and octyl; Branched alkyl groups such as isopropyl, isobutyl, sec-butyl and tert-butyl; And cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. The ratio of the hydrogen atoms of the alkyl groups substituted with fluorine atoms is usually 80 mol% or more, preferably 90 mol% or more, Is 100 mol%. When the substitution ratio of fluorine atoms is less than 80 mol%, the acid strength of the onium fluorinated alkyl fluorophosphate represented by the formula (c1) is lowered.

Particularly preferred R ^3c is a linear or branched perfluoroalkyl group having 1 to 4 carbon atoms and a substitution ratio of fluorine atoms of 100 mol%. 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) may be mentioned _{CF, (CF 3) 3 C} . The number j of R ^3c is an integer of 1 to 5, preferably 2 to 4, particularly preferably 2 or 3.

Preferred examples include a fluorinated phosphate anions specific alkyl-fluoro _{[(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} ] - of the may be mentioned, and these _{[(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 ] ^- is particularly preferred.

Preferred examples of the borate anion represented by the formula (c18) include tetrakis (pentafluorophenyl) borate ([B (C ₆ F ₅ ) ₄ ] ^- ), tetrakis [(trifluoromethyl) phenyl] B (C ₆ H ₄ CF ₃ ) ₄ ] ^- ), difluorobis (pentafluorophenyl) borate ([(C ₆ F ₅ ) ₂ BF ₂ ] ^- ), trifluoro (pentafluorophenyl) ([(C ₆ F ₅ ) BF ₃ ] ^- ) and tetrakis (difluorophenyl) borate ([B (C ₆ H ₃ F ₂ ) ₄ ] ^- ). Among them, tetrakis (pentafluorophenyl) borate ([B (C ₆ F ₅ ) ₄ ] ^- ) is particularly preferable.

(Trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [ 2- (2-furyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (Trichloromethyl) -6- [2- (5-ethyl-2-furyl) ethenyl] -s-triazine, 2,4- (Trichloromethyl) -6- [2- (3,5-dimethoxyphenyl) ethenyl] -s-triazine, (Trichloromethyl) -6- [2- (3,5-diethoxyphenyl) ethenyl] -s-triazine, 2,4-bis 2- (3-methoxy-5-ethoxyphenyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- 2- (3-methoxy-5-propoxyphenyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) (Trichloromethyl) -6- [2- (3,4-methylenedioxyphenyl) ethenyl] -s- (Trichloromethyl) -6- (3,4-methylenedioxyphenyl) -s-triazine, 2,4-bis-trichloromethyl-6- (3- (4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- Methyl-6- (2-bromo-4-methoxy) styrylphenyl-s-triazine, 2,4-bis- trichloromethyl-6- -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxynaphthyl) Bis (trichloromethyl) -1,3,5-triazine, 2- [2- (2-furyl) ethenyl] (Trichloromethyl) -1,3,5-triazine, 2- [2- (3,5-dimethoxyphenyl) (Trichloromethyl) -1,3,5-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (Trichloromethyl) -1,3,5-triazine, 2- (3,4-methylenedioxyphenyl) -4,6-bis (Trichloromethyl) -1,3,5-triazine, tris (1,3-dibromopropyl) -1,3,5-triazine, tris (2,3-dibromopropyl) Halogen-containing triazine compounds such as 3,5-triazine, and halogen-containing triazine compounds represented by the following formula (c3) such as tris (2,3-dibromopropyl) isocyanurate.

[14]

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

As the third embodiment of the component (C), α- (p-toluenesulfonyloxyimino) -phenylacetonitrile, α- (benzenesulfonyloxyimino) -2,4-dichlorophenylacetonitrile, α- Benzenesulfonyloxyimino) -2,6-dichlorophenylacetonitrile, a- (2-chlorobenzenesulfonyloxyimino) -4-methoxyphenylacetonitrile, a- (ethylsulfonyloxyimino) -1-cyclo Pentenylacetonitrile, and compounds represented by the following formula (c4) containing an oxime sulfonate group.

[Figure 15]

In the 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, Represents the number of repeating units of the structure in Fig.

In the formula (c4), the aromatic compound group represents a group of a compound which exhibits physical and chemical properties peculiar to an aromatic compound, and includes, for example, an aryl group such as a phenyl group or a naphthyl group or a heteroaryl group such as a furyl group or a thienyl group . These may have at least one substituent suitable for the cyclic structure, for example, a halogen atom, an alkyl group, an alkoxy group, and a nitro group. 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. Particularly, a compound wherein R ^12c is an aromatic compound group and R ^13c is an alkyl group having 1 to 4 carbon atoms is preferable.

As the acid generator represented by the 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 compound of a methyl group, specifically,? - (methylsulfonyloxy (Methylsulfonyloxyimino) -1- (p-methoxyphenyl) acetonitrile, and the like. , [2- (propylsulfonyloxyimino) -2,3-dihydroxothiophen-3-ylidene] (o-tolyl) acetonitrile. Specific examples of the photoacid generator represented by the formula (c4) when n = 2 include photoacid generators represented by the following formulas.

[16]

As the fourth embodiment of the component (C), there can be mentioned an onium salt having a naphthalene ring in its cation part. The term " having a naphthalene ring " means having a structure derived from naphthalene, meaning that at least two rings and such aromaticity are retained. The naphthalene ring may have a substituent such as a linear or branched alkyl group having 1 to 6 carbon atoms, a hydroxyl group, a linear or branched alkoxy group having 1 to 6 carbon atoms, and the like. The structure derived from the naphthalene ring may be monovalent (having one free valence) or two valences (having two free valences), but is preferably monovalent (except for the moiety bonded to the substituent) Quot; glass valence "). The number of naphthalene rings is preferably 1 to 3.

The cation moiety of the onium salt having a naphthalene ring in such a cation moiety is preferably a structure represented by the following formula (c5).

[Figure 17]

In the 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 is a linear or branched alkyl group having 1 to 6 carbon atoms, a phenyl group , 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 remaining two are each independently a straight or branched alkylene group having 1 to 6 carbon atoms, .

[Figure 18]

In the 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 alkyl group having 1 to 6 carbon atoms, and R ^19c denotes a Or a linear or branched alkylene 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, when a plurality of R < ^17c > exist, they may be the same or different. When there are a plurality of R ^18c , they may be the same or different.

The number of the groups represented by the formula (c6) among R ^14c , R ^15c and R ^16c is preferably one in view of the stability of the compound and the remainder is a linear or branched alkylene group having 1 to 6 carbon atoms, These ends may be combined to form a ring. In this case, the two alkylene groups constitute a 3- to 9-membered ring including a sulfur atom. The number of atoms (including sulfur atoms) constituting the ring is preferably 5 to 6.

Examples of the substituent that the alkylene group may have include an oxygen atom (in this case, forms a carbonyl group together with the carbon atom constituting the alkylene group), and a hydroxyl group.

Examples of the substituent which the phenyl group may have include a hydroxyl group, a linear or branched alkoxy group having 1 to 6 carbon atoms, a linear or branched alkyl group having 1 to 6 carbon atoms, and the like.

Preferable examples of these cationic moieties include those represented by the following formulas (c7) and (c8), and particularly preferred are structures represented by the following formula (c8).

[19]

The cationic moiety may be either an iodonium salt or a sulfonium salt, but a sulfonium salt is preferred from the viewpoint of acid generation efficiency and the like.

Therefore, an anion capable of forming a sulfonium salt is preferable as an anion moiety of an onium salt having a naphthalene ring at a cation moiety.

The anion moiety of such an acid generator is a fluoroalkylsulfonic acid ion or an arylsulfonic acid ion in which a part or all of hydrogen atoms are fluorinated.

The alkyl group in the fluoroalkylsulfonic acid ion may be in the form of a straight chain, branched or cyclic carbon number of 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, based on the volume of the generated acid and the diffusion distance thereof. Particularly, it is preferable that the diffusion region is branched or annular because the diffusion distance is short. In addition, a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group and the like are preferably used because they can be synthesized at low cost.

The aryl group in the aryl sulfonic 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 or may not be substituted with an alkyl group and a halogen atom. Particularly, an aryl group having 6 to 10 carbon atoms is preferable because it can be synthesized at low cost. Specific preferred examples include a phenyl group, a toluenesulfonyl group, an ethylphenyl group, a naphthyl group and a methylnaphthyl group.

In the fluoroalkylsulfonic acid ion or arylsulfonic acid ion, when the hydrogen atom is partially or totally fluorinated, the fluorination rate is preferably 10 to 100%, more preferably 50 to 100% Is replaced with a fluorine atom is preferable because the strength of the acid becomes strong. Specific examples thereof include trifluoromethanesulfonate, perfluorobutanesulfonate, perfluorooctanesulfonate, perfluorobenzenesulfonate, and the like.

Among these, preferable anion moieties include those 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).

[20]

In the formula (c10), x represents an integer of 1 to 4. In 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, and y is an integer of 1 to 3 Represents an integer. Of these, trifluoromethane sulfonate and perfluorobutane sulfonate are preferable from the viewpoint of safety.

As the anion moiety, those containing nitrogen represented by the following formulas (c13) and (c14) may also be used.

[Figure 21]

The equation (c13), (c14) of the, X ^c represents an alkylene group of a linear or branched, substituted with at least one hydrogen atom with a fluorine atom, the carbon number is 2-6 in the alkylene group, preferably from 3-5 , And most preferably 3 carbon atoms. Y ^c and Z ^c each independently represent a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom and the number of carbon atoms of the alkyl group is 1 to 10, preferably 1 to 7, more preferably 1 to 3.

The smaller the number of carbon atoms of the alkylene group of X ^c, or Y ^c, Z ^c alkyl group carbon atoms are preferred because good solubility in an organic solvent.

The alkyl group in the alkylene group or X ^c Y ^c, Z ^c, the more the number of hydrogen atoms being substituted by fluorine atoms, are preferable because the strength of the strong acid. The proportion of the fluorine atom in the alkylene group or the alkyl group, that is, the fluorine atom, is preferably 70 to 100%, more preferably 90 to 100%, and most preferably the perfluoroalkylene group in which all the hydrogen atoms are substituted with fluorine atoms A perfluoroalkyl group.

Preferred examples of the onium salt having a naphthalene ring in such a cation portion include compounds represented by the following formulas (c15) and (c16).

[22]

As the fifth embodiment of the component (C), bis (p-toluenesulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, Bis (2, 4-dimethylphenylsulfonyl) diazomethane, and other bis-sulfonyldiazomethanes; nitrobenzyl p-toluenesulfonate, 2,6-dinitrobenzyl p-toluenesulfonate, nitrobenzyl tosylate, dinitrobenzyl tosylate, nitrobenzylsulfonate, nitrobenzyl carbonate, dinitrobenzyl carb Nitrobenzyl derivatives such as Nate; Pyrogallol trimesilate, pyrogallol tristosylate, benzyltosylate, benzylsulfonate, N-methylsulfonyloxysuccinimide, N-trichloromethylsulfonyloxysuccinimide, N-phenylsulfonyloxymaleimide , Sulfonic acid esters such as N-methylsulfonyloxyphthalimide; Trifluoromethanesulfonic acid esters such as N-hydroxyphthalimide and N-hydroxynaphthalimide; (P-tert-butylphenyl) iodonium trifluoromethanesulfonate, diphenyl iodonium hexafluorophosphate, diphenyl iodonium hexafluorophosphate, (4-methoxyphenyl) phenyliodonium trifluoromethanesulfonate, bis Onium salts such as phosphonium hexafluorophosphate, (4-methoxyphenyl) diphenylsulfonium trifluoromethanesulfonate, and (p-tert-butylphenyl) diphenylsulfonium trifluoromethanesulfonate; Benzoin tosylates such as benzoin tosylate and? -Methyl benzoin tosylate; Other diphenyl iodonium salts, triphenylsulfonium salts, phenyldiazonium salts, and benzyl carbonate can be given.

The content of the component (C) in the positive-type photosensitive resin composition according to the present invention is not particularly limited within the range not impairing the object of the present invention, and is preferably 0.1 to 15 parts by weight per 100 parts by weight of the component (A) , More preferably 1 to 10 parts by weight.

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

The positive photosensitive resin composition of the present invention may further contain component (D). As a result, the resist pattern shape tends to be good, for example, the verticality of the side wall is high, and a resist pattern excellent in squareness is easily obtained. The reason why such effect is obtained is not clear, but it is presumed that the tertiary aliphatic amine can be uniformly dispersed in the resist film to effectively suppress the diffusion of acid generated from the component (C). Further, by containing the component (D), the elapse of time and stability of the positive-working photosensitive resin composition are likely to be improved. (D) may be used alone or in combination of two or more.

Various kinds of tertiary aliphatic amines have already been suggested, and any of the known tertiary aliphatic amines can be optionally used. For example, all three hydrogen atoms of ammonia NH ₃ are substituted with an alkyl group having 12 or less carbon atoms or an amine substituted with a hydroxyalkyl group Alkylamine or tri (alkyl alcohol) amine).

Specific examples of the trialkylamine include trimethylamine, triethylamine, tri- n -propylamine, tri-n-butylamine, tri-n-hexylamine, tri-n-pentylamine, n-octylamine, tri-n-nonylamine, tri-n-decaneylamine, tri-n-dodecylamine and the like.

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

The tertiary aliphatic amines may be used alone or in combination of two or more.

In the component (D), the proportion of the tertiary aliphatic amine is preferably 10 to 100% by weight, more preferably 50 to 100% by weight, and most preferably 100% by weight for the effect of the present invention.

In the present invention, a nitrogen-containing organic compound other than the tertiary aliphatic amine may be contained as the component (D) within the range that does not impair the effect of the present invention.

The nitrogen-containing organic compound other than the tertiary aliphatic amine is not particularly limited, and any known nitrogen-containing organic compound may be used. Specific examples thereof include cyclic amines, aliphatic amines other than tertiary aliphatic amines, and the like.

In the present invention, the term "aliphatic amine" means a linear amine having 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 ring structure in the molecule. The aliphatic group preferably has 1 to 12 carbon atoms.

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

The cyclic amine includes, for example, a heterocyclic compound containing a nitrogen atom as a hetero atom. The heterocyclic compound may be monocyclic (aliphatic monocyclic amine) or polycyclic (aliphatic polycyclic amine).

Specific examples of the aliphatic monocyclic amines include piperidine and piperazine.

As the aliphatic polycyclic amine, those having 6 to 10 carbon atoms are preferable, and specifically 1,5-diazabicyclo [4.3.0] -5-nonene, 1,8-diazabicyclo [5.4.0] Hexamethylenetetramine, 1,4-diazabicyclo [2.2.2] octane, and the like.

Examples of the aliphatic amines other than the tertiary aliphatic amine include amines (monoalkylamine or mono (alkyl alcohol) amine) in which one of the hydrogen atoms of ammonia NH ₃ is substituted with an alkyl group or hydroxyalkyl group having 12 or less carbon atoms; Amines (dialkylamine or di (alkyl alcohol) amine) in which two hydrogen atoms of ammonia NH ₃ are substituted with an alkyl group or hydroxyalkyl group having 12 or less carbon atoms. Specific examples of the monoalkylamine include n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, and n-decylamine.

Specific examples of dialkylamines include diethylamine, di-n-propylamine, di-n-heptylamine, di-n-octylamine and dicyclohexylamine.

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

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

The content of the component (D) in the positive-type photosensitive resin composition according to the present invention is 0.005 to 5.0 parts by weight per 100 parts by weight of the component (A) from the viewpoint that the effect of adding the component (D) More preferably 0.01 to 0.3 part by weight, and still more preferably 0.015 to 0.2 part by weight.

[Organic solvent (S)]

The positive photosensitive resin composition according to the present invention may contain an organic solvent (S). The inclusion of the organic solvent (S) makes it easy to adjust the coating properties of the positive photosensitive resin composition and the film thickness of the positive photosensitive resin composition layer formed using the positive photosensitive resin composition It is easy to get rid of. (S) 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; There may be mentioned ethylene glycol, ethylene glycol monoacetate, diethylene glycol, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, dipropylene glycol, and dipropylene glycol monoacetate, and monomethyl ether, monoethyl ether, , Monobutyl ether, or monophenyl ether (for example, propylene glycol monomethyl ether acetate), and derivatives thereof; Cyclic ethers such as dioxane; Examples of the solvent include ethyl formate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl pyruvate, ethoxyacetate, methyl methoxypropionate, ethyl ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl, 3-methoxybutyl acetate, Esters such as acetate; Aromatic hydrocarbons such as toluene and xylene; And the like.

The content of the organic solvent (S) in the positive photosensitive resin composition according to the present invention is preferably 50 to 3000 parts by weight, more preferably 100 to 2000 parts by weight, per 100 parts by weight of the component (A). When the content is within the above range, the applicability of the positive photosensitive resin composition tends to be improved, and the film thickness of the positive photosensitive resin composition layer formed using the positive photosensitive resin composition tends to be easily adjusted.

[Other components]

The positive photosensitive resin composition according to the present invention may further contain a polyvinyl resin in order to improve the reversibility of the film to be formed. Specific examples of the polyvinyl resin include polyvinyl chloride, polystyrene, polyhydroxystyrene, polyvinyl acetate, polyvinyl benzoic acid, polyvinyl methyl ether, polyvinyl ethyl ether, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl phenol, And copolymers thereof. The polyvinyl resin is preferably polyvinyl methyl ether because of its low glass transition point.

The positive photosensitive resin composition according to the present invention may further contain an adhesion promoter in order to improve the adhesiveness with the support.

The positive photosensitive resin composition according to the present invention may further contain a surfactant in order to improve coatability, defoaming property, leveling property and the like. Specific examples of the surfactant include BM-1000, BM-1100 (all manufactured by BM Chemical), Megafac F142D, Megafac F172, Megafac F173, Megafac F183 (both manufactured by Dainippon Ink & , Plurad FC-170C, Plurad FC-430, Plurad FC-431 (all from Sumitomo 3M), Sulphon S-112, Sulphon S-113, Sulphon S- Commercially available fluorinated surfactants such as Sulfol S-145 (all available from Asahi Glass Co.), SH-28PA, SH-190, SH-193, SZ-6032 and SF-8428 However, the present invention is not limited thereto.

The positive photosensitive resin composition according to the present invention may further contain an acid or an acid anhydride for finely adjusting the solubility in a developing solution.

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; Hydroxycinnamic acid, 3-hydroxycinnamic acid, 4-hydroxycinnamic acid, 5-hydroxycinnamic acid, 5-hydroxycinnamic acid, 5-hydroxybutyric acid, 3-hydroxybutyric acid, salicylic acid, - hydroxymonocarboxylic acids such as hydroxyisophthalic acid and cyclic acid; But are not limited to, oxalic, succinic, glutaric, adipic, maleic, itaconic, hexahydrophthalic, phthalic, isophthalic, terephthalic, 1,2- Polyvalent carboxylic acids such as tetracarboxylic acid, trimellitic acid, pyromellitic acid, cyclopentanetetracarboxylic acid, butanetetracarboxylic acid and 1,2,5,8-naphthalenetetracarboxylic acid; Wherein the acid anhydride is selected from the group consisting of maleic anhydride, itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenylsuccinic anhydride, tricarbamic acid anhydride, maleic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, Acid anhydrides such as tetracarboxylic acid anhydride, cyclopentanetetracarboxylic acid dianhydride, phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenone tetracarboxylic acid anhydride, trimellitate ethylene glycol bistrimic acid and trimellitate glycerin tris anhydride; And the like.

≪ Process for producing positive type photosensitive resin composition for producing micro lens pattern >

The positive photosensitive resin composition for producing a micro lens pattern according to the present invention can be prepared by mixing and stirring each of the above components in a usual manner and, if necessary, dispersing and dispersing them using a dispersing machine such as a dissolver, homogenizer, Mixing may be performed. Further, after mixing, it may be filtered using a mesh, a membrane filter or the like.

≪ Method of manufacturing microlens pattern >

The method for producing a micro lens pattern according to the present invention comprises the steps of forming a positive photosensitive resin composition layer for forming a positive photosensitive resin composition layer using the positive photosensitive resin composition according to the present invention; , A developing step of developing the exposed positive photosensitive resin composition layer, and a heating step of heating the developed positive photosensitive resin composition layer after development.

[Positive photosensitive resin composition layer forming step]

In the step of forming the positive photosensitive resin composition layer, the positive photosensitive resin composition layer is formed using the positive photosensitive resin composition according to the present invention. The positive photosensitive resin composition layer is preferably formed on a substrate. As the base material, for example, a lens material layer described later can be mentioned.

The method for forming the positive-type photosensitive resin composition layer is not particularly limited, and conventionally known methods can be used. When the positive photosensitive resin composition is a solid or highly viscous gel, for example, a predetermined amount of a positive photosensitive resin composition is supplied onto a substrate, and then the positive photosensitive resin composition is pressed by a method while appropriately heating the positive photosensitive resin composition Layer can be formed. In the case where the positive photosensitive resin composition is a liquid (for example, when the positive photosensitive resin composition contains an organic solvent (S)), for example, a contact transfer type application such as a roll coater, a reverse coater, a bar coater, A non-contact type coating device such as a spinner (rotary coating device) or a curtain flow coater is used to apply a positive photosensitive resin composition to a substrate so as to have a desired film thickness to form a coating film and heat treatment (prebaking Applied Bake (PAB)) treatment), the positive photosensitive resin composition layer can be formed by removing the organic solvent in the coating film.

The heating conditions vary depending on the kind of each component in the composition, the mixing ratio, the coating film thickness, etc., and the heating temperature is, for example, 60 to 150 DEG C (preferably 70 to 140 DEG C) For example, 0.5 to 60 minutes (preferably 1 to 50 minutes).

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

[Exposure step]

In the exposure step, the positive photosensitive resin composition layer is selectively exposed. The selective exposure can be carried out through a desired mask pattern, for example. The wavelength used for exposure is not particularly limited. The exposure can be carried out using radiation such as KrF excimer laser, ArF excimer laser, F ₂ excimer laser, EUV (extreme ultraviolet), VUV (vacuum ultraviolet), EB (electron beam), X-ray or soft X-ray. The positive photosensitive resin composition according to the present invention is particularly effective for a KrF excimer laser.

After the exposure, PEB treatment (post-exposure heat treatment) is appropriately performed. The conditions for the PEB treatment vary depending on the kind of each component in the composition, the mixing ratio, the coating film thickness, and the like. For example, the heating temperature is 60 to 150 占 폚 (preferably 70 to 140 占 폚) For 0.5 to 60 minutes (preferably 1 to 50 minutes).

[Development process]

In the developing step, the exposed positive photosensitive resin composition layer is developed. This dissolves and removes unnecessary parts.

Examples of the developer include aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di- Diethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7- undecene, 1,5- Diazabicyclo [4.3.0] -5-nonane, and the like can be used. 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 alkaline solution may be used as a developer. As the developing solution, 0.1 to 10 wt% aqueous solution of tetramethylammonium hydroxide is preferable.

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

After development, suitably wash with water for 30 to 90 seconds and dry using an air gun or oven.

[Heating process]

In the heating step, the positive photosensitive resin composition layer after development is heated. As a result, the positive photosensitive resin composition layer is thermally deformed to form a micro lens pattern, preferably a microlens pattern on a convex surface.

For example, the heating temperature is 130 to 170 占 폚 (preferably 140 to 160 占 폚), and the heating time is, for example, For about 1 to 30 minutes (preferably for 3 to 10 minutes).

≪ Method of Manufacturing Micro Lens >

The method of producing a micro lens pattern according to the present invention includes a positive photosensitive resin composition layer laminating step of laminating a positive photosensitive resin composition layer on a lens material layer using the positive photosensitive resin composition according to the present invention, A developing step of developing the positive photosensitive resin composition layer exposed, a step of heating the positive photosensitive resin composition layer after development to form a mask layer having a micro lens pattern And a shape transferring step of dry-etching the lens material layer and the mask layer to transfer the shape of the micro lens pattern to the lens material layer.

[Positive photosensitive resin composition layer laminating step]

In the step of laminating the positive photosensitive resin composition layer, the positive photosensitive resin composition layer is laminated on the lens material layer using the positive photosensitive resin composition according to the present invention. As the lens material layer, conventionally known ones can be used. For example, only a transparent flattening film or an antireflection film and a transparent flattening film are provided on a substrate such as a silicon wafer on which image elements are formed, and a lens material layer provided on the transparent flattening film .

The step of laminating the positive photosensitive resin composition layer is the same as the step of forming the positive photosensitive resin composition layer in the above-mentioned method of producing a micro lens pattern except that a lens material layer is used as a base material.

[Exposure step]

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

[Development process]

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

[Shape Transfer Process]

In the shape transfer process, the lens material layer and the mask layer are dry etched, and the shape of the micro lens pattern is transferred to the lens material layer. Thus, a microlens can be obtained from the lens material layer.

The dry etching is not particularly limited, and for example, dry etching by plasma (oxygen, argon, CF _4, etc.) or corona discharge can be used.

[ Example ]

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

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

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

(X, y, and z) attached to each repeating unit are the ratios (mol%) of the respective repeating units to the total repeating units contained in the resin in the following respective formulas shown in the following A-1 to A- to be.

A-1: Resin (weight average molecular weight 20,000, x = 70, y = 30) represented by the following formula:

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

[23]

A-2: Resin (weight average molecular weight: 8000, x = 75, y = 25)

[24]

A-3: Resin (weight average molecular weight: 20000, x = 70, y = 30)

[25]

A-4: Resin (Comparative Example, weight average molecular weight 10,000, x = 65, y = 25, z = 10)

[26]

B-1: Compound represented by the following formula

[Figure 27]

C-1: Compound represented by the following formula

[28]

C-2: Compound represented by the following formula

[29]

D-1: Triethylamine

D-2: Triethanolamine

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

<Evaluation>

[Resist pattern shape (evaluation of marginal resolution)] [

A positive photosensitive resin composition prepared in Example or Comparative Example was coated on a substrate having an antireflection film and an acrylic transparent flat film on a Si substrate using a spinner to form a coating film. The above-mentioned coating film was pre-baked on a hot plate at 100 DEG C for 90 seconds, and the coating film was dried to form a positive-type photosensitive resin composition layer having a thickness of 800 nm.

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

Thereafter, the positive photosensitive resin composition layer was subjected to PEB treatment at 110 캜 for 90 seconds, and then developed at 23 캜 in a 2.38% by weight aqueous solution of tetramethylammonium hydroxide for 60 seconds, And rinsed with pure water for 30 seconds. The pure water was poured off and dried to obtain a resist pattern.

The cross section of the obtained resist pattern was observed by SEM. The marginal resolution was obtained by varying the mask dimensions, and the marginal resolution was evaluated according to the following criteria. The results are shown in Table 2.

⊚ (very good): The critical resolution is 0.17 탆 or less

(Good): The critical resolution is more than 0.17 탆 and not more than 0.18 탆

? (Poor): The limit resolution is more than 0.18 탆 and not more than 0.19 탆

× (very bad): The limit resolution exceeds 0.19 μm

[Evaluation of resolution (width of white band)]

The resist pattern obtained in the same manner as above was observed with an SEM from above. The width of the white 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 dimension of the lower surface portion is larger than the dimension of the upper surface portion of the resist pattern. The width of the white band is the difference in dimension between the upper surface portion and the lower surface portion and indicates the degree of the tapered shape. The smaller the width of the white band, the better the verticality of the pattern.

⊚ (very good): Width of white band is less than 0.07 탆

(Good): Width of white band is 0.07 mu m or more and less than 0.075 mu m

? (Poor): Width of white band is 0.075 占 퐉 or more and less than 0.08 占 퐉

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

[Evaluation of Flowability (Flow Margin)]

The resist pattern obtained in the same manner as above was subjected to post-baking treatment at a temperature of 130 to 170 DEG C for 300 seconds at each temperature, and the cross section of the resist pattern was observed with an SEM. By the post-baking treatment, the lowest temperature T _{1 at} which the microlens patterns are formed and the lowest temperature T ₂ at which the lower portions of neighboring microlens patterns contact each other are obtained. The difference T ₂ -T ₁ was evaluated as a flow margin based on the following criteria. The results are shown in Table 2.

◎ ◎ (very good): Flow margin is 10 ℃ or more

(Good): Flow margin is 7 ° C or more and less than 10 ° C

○ (slightly fine): Flow margin is 4 ° C or more and less than 7 ° C

× (poor): Flow margin less than 4 ° C

As can be seen from Table 2, the compositions of Examples 1 to 7 containing the component (A) and the component (B) of the present invention all had excellent resolution and a wide flow margin. On the other hand, the compositions of Comparative Examples 1 to 3 which did not contain the component (A) and / or the component (B) of the present invention had a narrow flow margin.

Claims (9)

(A) containing an acid dissociable, dissolution inhibiting group and increasing the solubility in alkali by the action of an acid, a compound (B) having at least two vinyloxy groups, and a micro lens pattern A positive-working photosensitive resin composition for manufacturing,
The resin (A) comprises a structural unit (a1) derived from hydroxystyrene and a structural unit (a2) in which at least one hydrogen atom of a hydroxyl group in the structural unit derived from hydroxystyrene is substituted with an acid dissociable, dissolution inhibiting group- Wherein the resin (A1) is contained in the positive photosensitive resin composition. The method according to claim 1,
The resin (A1) has a weight average molecular weight of 5,000 to 30,000. The method according to claim 1,
The resin (A1) comprises a resin (A2) having a structural unit represented by the following formula (a1-1) and a structural unit represented by the following 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, R ^a4 represents an acid dissociable dissolution inhibiting group , p and r independently represent an integer of 1 to 5, q, s and t independently represent an integer of 0 to 4, provided that p + q and r + s + t are independently an integer of 1 to 5 to be) The method of claim 3,
(A3) having a structural unit represented by the formula (a1-1), a structural unit represented by the following formula (a2-2) and / or a structural unit represented by the following formula (a2-3) Wherein the positive photosensitive resin composition is a positive photosensitive resin composition.

(Wherein R ^a3 , R ^a5 , r, s, and t are as defined above, R ^a6 and R ^a7 independently represent a hydrogen atom or an alkyl group, R ^a8 and R ^a10 independently represent an alkyl group or a cycloalkyl group , R ^a9 represents a single bond or an alkylene group, provided that at least two of R ^a6 , R ^a7 and R ^a8 may be bonded to each other to form a ring) The method of claim 4,
The resin (A3) is preferably a resin (A4) having a structural unit represented by the formula (a1-1) and a structural unit represented by the formula (a2-2) and / or a structural unit And a resin (A5) having a structural unit represented by the above formula (a2-3). The method of claim 5,
Wherein the amount of the resin (A4) is 60 to 90 mol% based on the total amount of the resin (A4) and the resin (A5). The method according to claim 1,
(D) containing a tertiary aliphatic amine and a nitrogen-containing organic compound (D) containing a tertiary aliphatic amine. A positive photosensitive resin composition layer forming step of forming a positive photosensitive resin composition layer using the positive photosensitive resin composition of claim 1,
An exposure step of selectively exposing the positive photosensitive resin composition layer,
A developing step of developing the exposed positive photosensitive resin composition layer,
And heating the positive photosensitive resin composition layer after development. A positive type photosensitive resin composition layer laminating step of laminating a positive type photosensitive resin composition layer using the positive type photosensitive resin composition of claim 1 on a lens material layer,
An exposure step of selectively exposing the positive photosensitive resin composition layer,
A developing step of developing the exposed positive photosensitive resin composition layer,
A mask layer forming step of heating the positive photosensitive resin composition layer after development to form a mask layer having a micro lens pattern;
And a shape transfer step of dry-etching the lens material layer and the mask layer, and transferring the shape of the micro lens pattern to the lens material layer.