KR102624403B1 - Positive-type Photosensitive Resin Composition for Production of Microlens Pattern - Google Patents

Abstract

[Problem] To provide a positive type photosensitive resin composition for manufacturing a micro lens pattern that has both excellent resolution and a wide flow margin, a method for manufacturing a micro lens pattern using the same, and a method for manufacturing a micro lens.
[Solution] The positive photosensitive resin composition for producing a microlens pattern according to the present invention includes a resin (A) having an acid-dissociable, dissolution-inhibiting group and increasing solubility in alkali by the action of an acid, and at least two vinyloxy groups. It contains a compound (B) and a photoacid generator (C), wherein the resin (A) includes a structural unit (a1) derived from hydroxystyrene, and a hydrogen group of at least one hydroxyl group in the structural unit derived from hydroxystyrene. It includes a resin (A1) having a structural unit (a2) whose atoms are substituted with an acid-dissociable, dissolution-inhibiting group-containing group.

Description

Positive-type Photosensitive Resin Composition for Production of Microlens Pattern}

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

Solid-state imaging devices are used in conventional cameras, video cameras, etc. For this solid-state imaging device, a CCD (charge-coupled device) image sensor or a CMOS (complementary metal-oxide semiconductor) image sensor is used. The image sensor is equipped with a fine condensing lens (hereinafter referred to as a micro lens) for the purpose of improving light collection rate.

The microlens is formed, for example, by an etching method using a positive photosensitive resin composition. Specifically, a positive photosensitive resin composition layer is formed on the lens material layer using a positive photosensitive resin composition, and then this is selectively exposed. Next, after removing the exposed portion by development, the positive photosensitive resin composition layer is fluidized by heat treatment to form a mask layer having a micro lens pattern. Thereafter, 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, thereby obtaining a micro lens. Conventionally, as a positive type photosensitive resin composition for producing a micro lens pattern used to form the mask layer, for example, an acrylic or novolak type positive type resist material is used (Patent Document 1).

Japanese Patent Application Publication No. 2013-117662

The positive photosensitive resin composition for producing micro lens patterns as described above requires excellent resolution and a wide flow margin (temperature range capable of forming a good micro lens pattern), but the conventional positive photosensitive resin composition for producing micro lens patterns has these characteristics. There are not enough characteristics.

The present invention has been made in consideration of such conventional circumstances, and provides a positive-type photosensitive resin composition for manufacturing a micro lens pattern having both excellent resolution and a wide flow margin, a method for manufacturing a micro lens pattern using the same, and a method for manufacturing a micro lens. The purpose is to provide.

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

The first aspect of the present invention includes a resin (A) having an acid-dissociable, dissolution-inhibiting group and 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) contains a structural unit (a1) derived from hydroxystyrene, and a hydrogen atom of at least one hydroxyl group in the structural unit derived from hydroxystyrene. It is a positive type photosensitive resin composition containing 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 includes a positive photosensitive resin composition layer forming process of forming a positive photosensitive resin composition layer using the positive photosensitive resin composition, an exposure process of selectively exposing the positive photosensitive resin composition layer, A method for producing a micro lens pattern including 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 includes a positive photosensitive resin composition layer laminating process of laminating a positive photosensitive resin composition layer using the positive photosensitive resin composition on a lens material layer, and selectively exposing the positive photosensitive resin composition layer. An exposure process, a development process of developing the exposed positive photosensitive resin composition layer, a mask layer forming process of heating the developed positive photosensitive resin composition layer to form a mask layer having a micro lens pattern, and the lens. A method of manufacturing a micro lens including 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 type photosensitive resin composition for manufacturing a micro lens pattern having both excellent resolution and a wide flow margin, a method for manufacturing a micro lens pattern using the same, and a method for manufacturing a micro lens.

<Positive photosensitive resin composition for manufacturing micro lens patterns>

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

[Resin (A) which has an acid-dissociable, dissolution-inhibiting group and whose solubility in alkali increases due to the action of acid]

Resin (A), which has an acid-dissociable, dissolution-inhibiting group and whose solubility in alkali increases by the action of an acid, contains a structural unit (a1) derived from hydroxystyrene, and at least one hydroxyl group in the structural unit derived from hydroxystyrene. It includes a resin (A1) having a structural unit (a2) in which hydrogen atoms of are substituted with an acid-dissociable, dissolution-inhibiting group-containing group. Resin (A) can be used individually or in combination of two or more types.

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

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

[Tuesday 1]

(In the formula, 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, q, s, and t independently represent integers from 0 to 4, provided that p+q and r+s+t independently represent integers from 1 to 5. am)

In 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 for R ^a1 and R ^a3 is an alkyl group having 1 to 5 carbon atoms, preferably a straight-chain or branched alkyl group, and is methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, Pentyl group, isopentyl group, neopentyl group, etc. can be mentioned. Industrially, a methyl group is preferable. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., and a fluorine atom is particularly preferable. An alkyl group substituted with a halogen atom is one in which some or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms described above are substituted with halogen atoms. In the present invention, it is preferable that all hydrogen atoms are halogenated. The alkyl group substituted with a halogen atom is preferably a straight-chain or branched alkyl group substituted with a halogen atom, and in particular, fluorinated alkyl groups such as trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl group, and nonafluorobutyl group are more preferable, Trifluoromethyl group (-CF ₃ ) is most preferred. As R ^a1 and R ^a3 , a hydrogen atom or a methyl group is preferable, and a hydrogen atom is more preferable.

The alkyl groups 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 integers from 0 to 4. Among these, q, s, and t are preferably 0 or 1, and are particularly preferably 0 for industrial purposes. When q is 1, the substitution position of R ^a2 may be any of the o-position, m-position, and p-position, and when q is an integer of 2 to 4, any substitution position can be combined. When t is 1, the substitution position of R ^a5 may be any of the o-position, m-position, and p-position, and when t is an integer of 1 to 4, any substitution position can be combined. p and r represent an integer of 1 to 5, preferably an integer of 1 to 3, and preferably 1. When p and s are 1, the substitution position of the hydroxyl group may be any of the o-position, m-position, and p-position, but the p-position is preferable because it is easily available and low price. Additionally, when p is an integer of 2 to 5 and s is an integer of 2 to 4, arbitrary substitution positions can be combined.

Examples of the acid dissociable, dissolution inhibiting group represented by R ^a4 include groups represented by the following formula (a2-1-1), groups represented by the following formula (a2-1-2), and linear, branched, or cyclic groups having 1 to 6 carbon atoms. alkyl group, vinyloxyethyl group, tetrahydropyranyl group, tetrafuranyl group, or trialkylsilyl group.

[Tuesday 2]

In the above 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, and R ^a9 represents a single bond or an alkylene group, provided that at least two of R ^a6 , R ^a7 , and R ^a8 may combine with each other to form a ring.

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

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

Here, the acid dissociable, dissolution inhibiting group represented by the above formula (a2-1-1) is specifically methoxyethyl group, ethoxyethyl group, n-propoxyethyl group, isopropoxyethyl group, n-butoxyethyl group, and isobutoxy group. Examples include ethyl group, tert-butoxyethyl group, cyclohexyloxyethyl group, methoxypropyl group, ethoxypropyl group, 1-methoxy-1-methyl-ethyl group, and 1-ethoxy-1-methylethyl group. Additionally, examples of the acid dissociable, dissolution inhibiting group represented by the above formula (a2-1-2) include tert-butoxycarbonyl group, tert-butoxycarbonylmethyl group, etc. In addition, 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 structural units (a1) and (a2) can be used one type or in mixture of two or more types.

In the resin (A1), the total ratio of the structural units (a1) and (a2) is preferably 10 to 100 mol%, and more preferably 30 to 100 mol%, relative to the total structural units constituting the resin (A1). 50 to 100 mol% is more preferable, 70 to 100 mol% is particularly preferable, and 100 mol% is most preferable. If the ratio is within the above range, the resulting positive photosensitive resin composition tends to have superior resolution, a wider flow margin can easily be secured, and the balance with other structural units is good.

Of the total of structural units (a1) and (a2), the proportion of structural unit (a2) (i.e., protection rate of hydroxystyrene) is preferably 10 to 60 mol%, and more preferably 20 to 40 mol%. . When the protection rate of hydroxystyrene is within the above range, the obtained positive photosensitive resin composition tends to have excellent resolution and a wider flow margin is likely to be secured.

(different building blocks)

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

·Constitutive unit (a3)

The structural unit (a3) is a structural unit derived from styrene. By containing the structural unit (a3) and adjusting its content, there are cases where the solubility of the resin (A1) in an alkaline developer can be adjusted, and the alkali solubility of the thick resist film can be controlled accordingly. There are cases where the shape can be further improved.

Here, the term “styrene” includes styrene in the narrow sense, styrene in the narrow sense in which the hydrogen atom at the α position is replaced by another substituent such as a halogen atom, an alkyl group, or a halogenated alkyl group, and such derivatives. “Structural unit derived from styrene” means a structural unit formed by cleavage of the ethylenic double bond of styrene. In styrene, the hydrogen atom of the phenyl group may be substituted with a substituent such as a lower alkyl group (for example, an alkyl group having 1 to 5 carbon atoms).

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

[Tuesday 3]

In the formula, 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.

Examples of R include the same groups as those exemplified for R ^a1 and R ^a3 above. Examples of R ⁷ include the same groups as those exemplified for R ^a2 and R ^a5 above.

r is an integer from 0 to 3. Among these, r is preferably 0 or 1, and is particularly preferably 0 for industrial reasons.

When r is 1, the substitution position of R ⁷ may be any of the o-position, m-position, and p-position, and when r is 2 or 3, any substitution position can be combined.

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

In the resin (A1), the ratio of the structural unit (a3) is preferably 0 to 90 mol%, more preferably 0 to 70 mol%, and 0 to 50 mol% relative to all structural units constituting the resin (A1). Mol% is more preferable, 0 to 30 mol% is particularly preferable, and 0 mol% is most preferable. If the ratio is within the above range, the balance with other structural units is likely to be good. The lower limit of the ratio is preferably 1 mol%, more preferably 3 mol%, and particularly preferably 5 mol%, based on the total structural units constituting the resin (A1). If the lower limit is the above value, the effect of having the structural unit (a3) is likely to increase.

·Constitutive unit (a4)

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

As a preferable structural unit (a4), a structural unit having a chain-shaped 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.

If the structural unit (a4) has a structural unit derived from an acrylic acid ester having an alcoholic hydroxyl group-containing cyclic alkyl group (hereinafter sometimes simply referred to as a “structural unit having a hydroxyl group-containing cyclic alkyl group”), resolution may increase. In some cases, etching resistance also improves.

In addition, if the structural unit (a4) has a structural unit derived from an acrylic acid ester having an alcoholic hydroxyl group-containing chain alkyl group (hereinafter, it may simply be referred to as a “structural unit having a hydroxyl group-containing chain alkyl group”), (A) component In some cases, the overall hydrophilicity increases, and in some cases, the affinity with the developer increases, thereby improving resolution.

··Constitutive unit 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 the ester group [-C(O)O-] of acrylic acid ester. Here, “hydroxyl group-containing cyclic alkyl group” is a group in which a hydroxyl group is bonded to a cyclic alkyl group.

It is preferable that 1 to 3 hydroxyl groups are bonded, for example, and it is more preferable that 1 hydroxyl group is bonded.

The cyclic alkyl group may be monocyclic or polycyclic, but is preferably a polycyclic group. Moreover, it is preferable that the carbon number of a cyclic alkyl group is 5-15.

Specific examples of cyclic alkyl groups include the following.

Examples of monocyclic cyclic alkyl groups include groups obtained by removing 1 to 4 hydrogen atoms from cycloalkane. More specifically, monocyclic cyclic alkyl groups include groups obtained by removing 1 to 4 hydrogen atoms from cycloalkanes such as cyclopentane and cyclohexane, and among these, cyclohexyl group is preferable.

Examples of polycyclic cyclic alkyl groups include groups obtained by removing 1 to 4 hydrogen atoms from polycycloalkanes such as bicycloalkanes, tricycloalkanes, and tetracycloalkanes. More specifically, groups obtained by removing 1 to 4 hydrogen atoms from polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane can be mentioned.

In addition, such cyclic alkyl groups can be appropriately selected and used from among many proposed as constituting acid-dissociable, dissolution-inhibiting groups in, for example, resins for photoresist compositions for ArF excimer laser processes. Among these, cyclohexyl group, adamantyl group, norbornyl group, and tetracyclododecanyl group are industrially available and preferred.

Among these exemplified monocyclic groups and polycyclic groups, cyclohexyl group and adamantyl group are preferable, and adamantyl group is especially preferable.

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

[Tuesday 4]

In the formula, 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.

Examples of R include the same groups as those exemplified for R ^a1 and R ^a3 above.

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

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

··Constitutive unit having a hydroxyl group-containing chain alkyl group

Examples of the structural unit having a hydroxyl-containing chain alkyl group include a structural unit in which a chain-shaped hydroxyalkyl group is bonded to the ester group [-C(O)O-] of acrylic acid ester. Here, “chain-shaped hydroxyalkyl group” means a group in which some or all of the hydrogen atoms in a chain-shaped (linear or branched) alkyl group are replaced with hydroxyl groups.

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

[Tuesday 5]

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

Examples of R include the same groups as those exemplified for R ^a1 and R ^a3 above.

The hydroxyalkyl group for R ⁸ is preferably a hydroxyalkyl group with 1 to 10 carbon atoms, more preferably a hydroxyalkyl group with 2 to 8 carbon atoms, and even more preferably a linear hydroxyalkyl group with 2 to 4 carbon atoms. .

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

The structural unit (a4) can be used alone or in a mixture of two or more types.

In the resin (A1), the ratio of the structural unit (a4) is preferably 0 to 90 mol%, more preferably 0 to 70 mol%, and 0 to 50 mol% relative to all structural units constituting the resin (A1). Mol% is more preferable, 0 to 30 mol% is particularly preferable, and 0 mol% is most preferable. If the ratio is within the above range, the balance with other structural units is likely to be good. The lower limit of the ratio is preferably 1 mol%, more preferably 3 mol%, and particularly preferably 5 mol%, based on the total structural units constituting the resin (A1). If the lower limit is the above value, the effect of having the structural unit (a4) is likely to increase.

Resin (A1) may contain structural units (a5) other than the structural units (a1) to (a4) as long as the effect of the present invention is not impaired.

The structural unit (a5) is not particularly limited as long as it is another structural unit that is not classified into the structural units (a1) to (a4) described above, and is used for ArF excimer lasers or KrF positive excimer lasers (preferably for KrF excimer lasers). Many of those conventionally known to be used in resist resins such as these can be used.

Resin (A1) may be used alone or in combination of two or more types.

Among the components (A), the proportion of 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.

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

[Tuesday 6]

(In the formula, 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 photosensitive resin composition is likely to have superior resolution and a wider flow margin is likely to be secured.

Resin (A2) may be used alone or in combination of two or more types.

The proportion of resin (A2) in 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.

Resin (A2) is a resin (A3) having a structural unit represented by the above 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). It is desirable to include it.

[Tuesday 7]

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

When the resin (A2) contains the resin (A3), the resulting positive photosensitive resin composition is likely to have superior resolution and a wider flow margin is likely to be secured.

Resin (A3) may be used individually or in combination of two or more types.

The proportion of resin (A3) in 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.

Resin (A3) is a resin (A4) having a structural unit represented by the formula (a1-1), a structural unit represented by the formula (a2-2), and/or a structural unit represented by the formula (a1-1). , it is preferable to include 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 photosensitive resin composition is likely to have much more excellent resolution and a wider flow margin is likely to be secured.

In particular, when the resin (A3) contains both the resin (A4) and the resin (A5), it is preferable because it is easy to achieve both high resolution and wide flow margin.

Each of Resin (A4) and Resin (A5) may be used individually or in combination of two or more types.

In the resin (A3), the total ratio of resins (A4) and (A5) 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. %am.

The amount of Resin (A4) is preferably 60 to 90 mol%, and more preferably 70 to 80 mol%, relative to the total of Resin (A4) and Resin (A5). If the amount of resin (A4) is within the above range, the obtained positive photosensitive resin composition is likely to have particularly excellent resolution, and a particularly wide flow margin is likely to be secured.

The weight average molecular weight (Mw) of the resin (A1) is preferably 5,000 to 30,000. The same applies to the weight average molecular weights of resins (A2) and (A3). If the weight average molecular weight is within the above range, the resulting positive photosensitive resin composition tends to have good resolution, heat resistance, and flow properties. In addition, in this specification, the weight average molecular weight refers to polystyrene conversion by gel permeation chromatography (GPC).

The weight average molecular weight of the resin (A4) is preferably 15,000 to 30,000, and more preferably 17,000 to 25,000. If the weight average molecular weight is 15000 or more, the heat resistance of the resulting positive photosensitive resin composition is likely to be improved, and since the flow property is only increased, a wide flow margin is likely to be secured. On the other hand, if the weight average molecular weight is 30000 or less, the resulting positive photosensitive resin composition is likely to have excellent resolution.

The weight average molecular weight of resin (A5) is preferably 5,000 to 15,000, and more preferably 7,000 to 10,000. If the weight average molecular weight is within the above range, the resulting positive photosensitive resin composition tends to have good heat resistance and flow properties.

In the present invention, the component (A) may contain, in addition to the resin (A1), resins generally used as resins for chemically amplified positive resists, such as PHS resins and acrylic resins, to the extent that the effects of the present invention are not impaired. do.

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

In the positive photosensitive resin composition of the present invention, the content of component (A) may be adjusted according to the resist film thickness 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 the oxygen atom of the vinyloxy group (CH ₂ =CH-O-) is bonded to a carbon atom. By containing such a compound, the obtained positive photosensitive resin composition is likely to have excellent resolution and a wide flow margin is likely to be secured. (B) Component can be used individually or in combination of two or more types.

It is presumed that compound (B), which has at least two vinyloxy groups, exerts the above effect by acting as a crosslinking agent for component (A). That is, the compound (B) having at least two vinyloxy groups undergoes a crosslinking reaction with component (A) by heating during prebaking, forming an alkali-insolubilized resist layer over the entire substrate. Afterwards, the cross-linking is decomposed by the action of the acid generated from component (B) during exposure, and the exposed portion changes to alkali-soluble, while the unexposed portion remains alkali-insoluble, so it is assumed that the dissolution contrast is improved. Additionally, it is presumed that the flow margin improves as crosslinking with the resin (A) further progresses during post-baking.

As the compound (B) having at least two vinyloxy groups, a number of compounds are specifically listed in Japanese Patent Application Laid-Open No. Hei 6-148889, Japanese Patent Application Laid-Open No. 6-230574, etc., and can be arbitrarily selected from among these for use. In particular, considering the resist profile shape due to thermal crosslinkability and decomposability by acid, and the characteristics of the contrast between exposed and unexposed areas, some or all of the hydroxyl groups of the alcohol represented by the general formula (f-2) below are used. Compounds etherified by substituting a hydrogen atom with a vinyl group are preferred.

Rb-(OH) _b (f-2)

In the formula, Rb is a group in which b hydrogen atoms have been removed from a linear, branched, or cyclic alkane, and may have a substituent. Additionally, an oxygen bond (ether bond) may exist in the alkane. b represents 2, 3, or 4.

Specifically, 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, etc. I can hear it.

As the compound (B) having at least two vinyloxy groups, one represented by the following general formula (f-3) is also preferable.

CH ₂ =CH-OR ²⁷ -O-CH=CH ₂ (f-3)

In 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 general formula (f-4). R ²⁷ may have a substituent. Additionally, R ²⁷ may contain an oxygen bond (ether bond) in the main chain.

[Tuesday 8]

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

As R ²⁷ , -C ₄ H ₈ -, -C ₂ H ₄ OC ₂ H ₄ -, -C ₂ H ₄ OC ₂ H ₄ OC ₂ H ₄ -, groups represented by general formula (f-4), etc. are preferable. , Among them, the group represented by the general formula (f-4) is preferable, and in particular, the group represented by the general formula (f-4) in which R ²⁸ is an alkylene group (i.e., methylene group) having 1 carbon atom and c is 1 is preferable.

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

In the positive photosensitive resin composition according to the present invention, the content of component (B) is 0.1 to 15 parts by weight based on 100 parts by weight of component (A), since the resolution and flow margin of the resulting positive photosensitive resin composition are likely to be improved. Parts by weight are preferable, and 1 to 8 parts by weight are more preferable.

[Mine generator (C)]

The photoacid generator (C) used in the present invention is not particularly limited as long as it is a compound that generates an acid upon irradiation of actinic light or radiation. (C) Component can be used individually or in combination of two or more types.

(C) As the component, the photoacid generator of the first to fifth aspects described below is preferable. Hereinafter, preferred components (C) will be described as first to fifth aspects.

(C) As a 1st aspect in component, the compound represented by the following formula (c1) is mentioned.

[Tuesday 9]

In the above formula (c1), X ^1c represents a sulfur atom or an iodine atom with valence g, and g is 1 or 2. h represents the number of repeat units of the structure within the parentheses. R ^1c is ^an organic group bonded to Represents an alkynyl group, and R ^1c is alkyl, hydroxy, alkoxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, arylthiocarbonyl, acyloxy, arylthio, alkylthio, aryl, heterocyclic ring. , aryloxy, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, alkyleneoxy, amino, cyano, nitro, 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 R ^1c are directly connected to each other, or -O-, -S-, -SO-, -SO ₂ -, -NH-, -NR ^2c -, -CO-, -COO-, -CONH-, A ring structure containing X ^1c may be formed by bonding through an alkylene group having 1 to 3 carbon atoms or a phenylene group. 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).

[Tuesday 10]

In the above formula (c2 ^{) ,} , alkoxy having 1 to 8 carbon atoms, aryl, hydroxy, cyano, and nitro groups having 6 to 10 carbon atoms, and halogen. X ^5C is -o-, -S-, -SO-, -SO _2- , -NH-, -NR ^2C- , -co-, -COO-, -CONH- Represents a phenylene group. h represents the number of repeat units of the structure within the parentheses. h+1 X ^4c and h X ^5c may be the same or different. R ^2c is as defined above.

X ^{3c -} is a counter ion of onium, and examples include a fluorinated alkyl fluorophosphoric acid anion represented by the following formula (c17) or a borate anion represented by the following formula (c18).

[Tuesday 11]

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

[Tuesday 12]

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

Examples of the onium ion in the compound represented by the formula (c1) include triphenylsulfonium, tri-p-tolylsulfonium, 4-(phenylthio)phenyldiphenylsulfonium, and bis[4-(diphenylsulfonio)phenyl]. Sulfide, bis[4-{bis[4-(2-hydroxyethoxy)phenyl]sulfonio}phenyl]sulfide, bis{4-[bis(4-fluorophenyl)sulfonio]phenyl} Sulfide, 4-(4-benzoyl-2-chlorophenylthio)phenylbis(4-fluorophenyl)sulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracene-2 -yldi-p-tolylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracene-2-yldiphenylsulfonium, 2-[(diphenyl)sulfonio]thioxane ton, 4-[4-(4-tert-butylbenzoyl)phenylthio]phenyldi-p-tolylsulfonium, 4-(4-benzoylphenylthio)phenyldiphenylsulfonium, diphenylphenacilsulfonium, 4- Hydroxyphenylmethylbenzylsulfonium, 2-naphthylmethyl(1-ethoxycarbonyl)ethylsulfonium, 4-hydroxyphenylmethylphenacilsulfonium, phenyl[4-(4-biphenylthio)phenyl]4- Biphenylsulfonium, phenyl[4-(4-biphenylthio)phenyl]3-biphenylsulfonium, [4-(4-acetophenylthio)phenyl]diphenylsulfonium, octadecylmethylphenacilsulfonium, di Phenyliodonium, di-p-tolyliodonium, bis(4-dodecylphenyl)iodonium, bis(4-methoxyphenyl)iodonium, (4-octyloxyphenyl)phenyliodonium, Bis(4-decyloxy)phenyliodonium, 4-(2-hydroxytetradecyloxy)phenylphenyliodonium, 4-isopropylphenyl(p-tolyl)iodonium, or 4-isobutyl Phenyl (p-tolyl) iodonium, etc. can be mentioned.

Among the onium ions in the compound represented by the formula (c1), a sulfonium ion represented by the formula (c19) below is a preferred onium ion.

[Tuesday 13]

In the above formula (c19), R ^8c is each independently hydrogen atom, alkyl, hydroxy, alkoxy, alkylcarbonyl, alkylcarbonyloxy, alkyloxycarbonyl, halogen atom, aryl, arylcarbonyl which may have a substituent. It represents a group selected from the group consisting of. X ^2c has the same meaning as X ^2c in the above formula (c1).

Specific examples of the sulfonium ion represented by the formula (c19) include 4-(phenylthio)phenyldiphenylsulfonium, 4-(4-benzoyl-2-chlorophenylthio)phenylbis(4-fluorophenyl)sulfonium, 4-(4-benzoylphenylthio)phenyldiphenylsulfonium, phenyl[4-(4-biphenylthio)phenyl]4-biphenylsulfonium, phenyl[4-(4-biphenylthio)phenyl]3- Examples include biphenylsulfonium, [4-(4-acetophenylthio)phenyl]diphenylsulfonium, and diphenyl[4-(p-terphenylthio)phenyl]diphenylsulfonium.

In the fluorinated alkylfluorophosphoric acid anion represented by the above formula (c17), R ^3c represents an alkyl group substituted with a fluorine atom, preferably has 1 to 8 carbon atoms, and more preferably has 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; Also included are cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl, and the ratio of hydrogen atoms in the alkyl group to fluorine atoms is usually 80 mol% or more, preferably 90 mol% or more, and 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 above formula (c1) decreases.

Particularly preferred R ^3c is a linear or branched perfluoroalkyl group having 1 to 4 carbon atoms and a fluorine atom substitution rate of 100 mol%, and specific examples 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 preferred fluorinated alkylfluorophosphoric acid anions 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 ] ^- can be mentioned, and among 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 specific examples of the borate anion represented by the formula (c18) include tetrakis(pentafluorophenyl)borate ([B(C ₆ F ₅ ) ₄ ] ^- ), tetrakis[(trifluoromethyl)phenyl]borate ([ B(C ₆ H ₄ CF ₃ ) ₄ ] ^- ), difluorobis(pentafluorophenyl)borate ([(C ₆ F ₅ ) ₂ BF ₂ ] ^- ), trifluoro(pentafluorophenyl)borate ([(C ₆ F ₅ )BF ₃ ] ^- ), tetrakis(difluorophenyl)borate ([B(C ₆ H ₃ F ₂ ) ₄ ] ^- ), etc. Among these, tetrakis(pentafluorophenyl)borate ([B(C ₆ F ₅ ) ₄ ] ^- ) is particularly preferable.

(C) As a second aspect in component, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[ 2-(2-furyl)ethenyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methyl-2-furyl)ethenyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-ethyl-2-furyl)ethenyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2- (5-propyl-2-furyl)ethenyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,5-dimethoxyphenyl)ethenyl]-s-tri Azine, 2,4-bis(trichloromethyl)-6-[2-(3,5-diethoxyphenyl)ethenyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[ 2-(3,5-dipropoxyphenyl)ethenyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(3-methoxy-5-ethoxyphenyl) thennyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(3-methoxy-5-propoxyphenyl)ethenyl]-s-triazine, 2,4-bis (trichloromethyl)-6-[2-(3,4-methylenedioxyphenyl)ethenyl]-s-triazine, 2,4-bis(trichloromethyl)-6-(3,4-methylenedi Oxyphenyl)-s-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)phenyl-s-triazine, 2,4-bis-trichloromethyl-6 -(2-Bromo-4-methoxy)phenyl-s-triazine, 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(trichlor Romethyl)-1,3,5-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-[2-( 2-furyl)ethenyl]-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-[2-(5-methyl-2-furyl)ethenyl]-4,6- Bis(trichloromethyl)-1,3,5-triazine, 2-[2-(3,5-dimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-1,3,5 -Triazine, 2-[2-(3,4-dimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4-methylene Dioxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, tris(1,3-dibromopropyl)-1,3,5-triazine, tris(2, Halogen-containing triazine compounds such as 3-dibromopropyl)-1,3,5-triazine, and halogens represented by the following formula (c3) such as tris(2,3-dibromopropyl)isocyanurate and triazine-containing compounds.

[Tuesday 14]

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

Moreover, as the third aspect in component (C), α-(p-toluenesulfonyloxyimino)-phenylacetonitrile, α-(benzenesulfonyloxyimino)-2,4-dichlorophenylacetonitrile, α-( Benzenesulfonyloxyimino)-2,6-dichlorophenylacetonitrile, α-(2-chlorobenzenesulfonyloxyimino)-4-methoxyphenylacetonitrile, α-(ethylsulfonyloxyimino)-1-cyclo Pentenylacetonitrile, and a compound represented by the following formula (c4) containing an oxime sulfonate group can be mentioned.

[Tuesday 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, unsaturated hydrocarbon group, or aromatic compound group, and n is in parentheses. Indicates the number of repeating units of the structure within.

In the formula (c4), the aromatic compound group refers to a group of a compound that exhibits physical and chemical properties unique to aromatic compounds, and examples include aryl groups such as phenyl groups and naphthyl groups, and heteroaryl groups such as furyl groups and thienyl groups. You can. These may have one or more suitable cyclic substituents, such as a halogen atom, an alkyl group, an alkoxy group, or a nitro group. Moreover, R ^13c is particularly preferably an alkyl group having 1 to 6 carbon atoms, and examples thereof include methyl group, ethyl group, propyl group, and butyl group. In particular, compounds in which R ^12c is an aromatic compound group and R ^13c is an alkyl group having 1 to 4 carbon atoms are preferable.

The acid generator represented by the above formula (c4) is a compound where, when n=1, R ^12c is any one of a phenyl group, methylphenyl group, and methoxyphenyl group, and R ^13c is a methyl group, specifically, α-(methylsulfonyloxyi). Mino)-1-phenylacetonitrile, α-(methylsulfonyloxyimino)-1-(p-methylphenyl)acetonitrile, α-(methylsulfonyloxyimino)-1-(p-methoxyphenyl)acetonitrile , [2-(propylsulfonyloxyimino)-2,3-dihydroxythiophen-3-ylidene](o-tolyl)acetonitrile, etc. When n=2, the photo acid generator represented by the above formula (c4) specifically includes a photo acid generator represented by the following formula.

[Tuesday 16]

Moreover, as a fourth aspect in component (C), an onium salt having a naphthalene ring in the cation portion can be mentioned. “Having a naphthalene ring” means having a structure derived from naphthalene, and means maintaining the structure of at least two rings and such aromaticity. This naphthalene ring may have a substituent such as a straight-chain or branched alkyl group having 1 to 6 carbon atoms, a hydroxyl group, or a straight-chain or branched alkoxy group having 1 to 6 carbon atoms. The structure derived from the naphthalene ring may be a monovalent group (one free valence) or a bivalent group (two free valences) or more, but it is preferable to be a monovalent group (however, excluding the part that bonds to the substituent above) (counting free valences). The number of naphthalene rings is preferably 1 to 3.

As the cation portion of the onium salt having a naphthalene ring in such a cation portion, the structure represented by the following formula (c5) is preferable.

[Tuesday 17]

In the formula (c5), at least one of R ^14c , R ^15c , and R ^16c represents a group represented by the formula (c6) below, and the remainder is a linear or branched alkyl group having 1 to 6 carbon atoms, or a phenyl group that may have a substituent. , a hydroxyl group, or a linear or branched alkoxy group having 1 to 6 carbon atoms. Alternatively, one of R ^14c , R ^15c , and R ^16c is a group represented by the formula (c6) below, and the remaining two are each independently a linear or branched alkylene group having 1 to 6 carbon atoms, and these terminals are combined to form a ring. It can be done.

[Tuesday 18]

In the above formula (c6), R ^17c and R ^18c each independently represent a hydroxyl group, a straight-chain or branched alkoxy group having 1 to 6 carbon atoms, or a straight-chain or branched alkyl group having 1 to 6 carbon atoms, and R ^19c is simply It represents a linear or branched alkylene group with 1 to 6 carbon atoms that may have a bond or substituent. l and m each independently represent integers from 0 to 2, and l+m is 3 or less. However, when there are two or more R ^17cs , they may be the same or different from each other. Moreover, when multiple R ^18c exists, they may be the same or different from each other.

Among R ^14c , R ^15c , and R ^16c , the number of groups represented by the formula (c6) is preferably one from the viewpoint of stability of the compound, and the remainder are linear or branched alkylene groups having 1 to 6 carbon atoms, These terminals 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.

Additionally, substituents that the alkylene group may have include an oxygen atom (in this case, it forms a carbonyl group together with the carbon atom constituting the alkylene group), a hydroxyl group, and the like.

Additionally, substituents that the phenyl group may have include a hydroxyl group, a straight-chain or branched alkoxy group having 1 to 6 carbon atoms, and a straight-chain or branched alkyl group having 1 to 6 carbon atoms.

Preferred examples of these cationic moieties include those represented by the following formulas (c7) and (c8), and the structure represented by the following formula (c8) is particularly preferable.

[Tuesday 19]

Such a cation moiety may be either an iodonium salt or a sulfonium salt, but a sulfonium salt is preferable in terms of acid generation efficiency and the like.

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

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

The alkyl group in the fluoroalkyl sulfonic acid ion may be linear, branched, or cyclic with 1 to 20 carbon atoms, and is preferably 1 to 10 carbon atoms in view of the large volume of the acid generated and its diffusion distance. In particular, branched or circular shapes are preferable because the diffusion distance is short. Moreover, in view of their ability to be synthesized at low cost, methyl group, ethyl group, propyl group, butyl group, octyl group, etc. are mentioned as preferable ones.

The aryl group in the arylsulfonic acid ion is an aryl group having 6 to 20 carbon atoms, and examples include an alkyl group, a phenyl group, and a naphthyl group that may or may not be substituted with a halogen atom. In particular, an aryl group having 6 to 10 carbon atoms is preferable because it can be synthesized at low cost. Preferred examples include phenyl group, toluenesulfonyl group, ethylphenyl group, naphthyl group, and methylnaphthyl group.

In the above fluoroalkylsulfonic acid ion or arylsulfonic acid ion, when part or all of the hydrogen atoms are fluorinated, the fluorination rate is preferably 10 to 100%, more preferably 50 to 100%, and especially the hydrogen atom. It is preferable that all of are replaced with fluorine atoms because the strength of the acid becomes stronger. Specific examples of such include trifluoromethane sulfonate, perfluorobutane sulfonate, perfluorooctane sulfonate, and perfluorobenzene sulfonate.

Among these, preferred 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 formula (c10) or (c11), or a group represented by the following formula (c12).

[Tuesday 20]

In the above formula (c10), x represents an integer of 1 to 4. Moreover, in the above formula (c11), R ^21c represents a hydrogen atom, a hydroxyl group, a straight-chain or branched alkyl group with 1 to 6 carbon atoms, or a straight-chain or branched alkoxy group with 1 to 6 carbon atoms, and y represents 1 to 3 carbon atoms. Represents an integer. Among these, trifluoromethane sulfonate and perfluorobutane sulfonate are preferable from the viewpoint of safety.

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

[Tuesday 21]

In the above ^formulas (c13) and (c14), , and most preferably has 3 carbon atoms. In addition, Y ^c and Z ^c each independently represent a linear or branched alkyl group in which at least one hydrogen atom is replaced with a fluorine atom, and the carbon number of the alkyl group is 1 to 10, preferably 1 to 7, more preferably 1 to 7. It is 1 to 3.

The smaller the carbon number of ^{the alkylene} group ^of

Additionally, the greater the number of hydrogen atoms substituted ^with fluorine atoms in the ^alkylene group ^of The proportion of fluorine atoms in the alkylene group or alkyl group, that is, the fluorination rate, is preferably 70 to 100%, more preferably 90 to 100%, and most preferably a perfluoroalkylene group in which all hydrogen atoms are replaced with fluorine atoms, or It is a perfluoroalkyl group.

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

[Tuesday 22]

Moreover, as the fifth aspect in component (C), bis(p-toluenesulfonyl)diazomethane, bis(1,1-dimethylethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, Bissulfonyldiazomethane such as bis(2,4-dimethylphenylsulfonyl)diazomethane; 2-nitrobenzyl p-toluenesulfonic acid, 2,6-dinitrobenzyl p-toluenesulfonic acid, nitrobenzyl tosylate, dinitrobenzyl tosylate, nitrobenzylsulfonate, nitrobenzyl carbonate, dinitrobenzylcarbohydrate Nitrobenzyl derivatives such as Nate; Pyrogallol trimesylate, pyrogallol tritosylate, benzyl tosylate, benzyl sulfonate, N-methylsulfonyloxysuccinimide, N-trichloromethylsulfonyloxysuccinimide, N-phenylsulfonyloxymaleimide , sulfonic acid esters such as N-methylsulfonyloxyphthalimide; Trifluoromethanesulfonic acid esters such as N-hydroxyphthalimide and N-hydroxynaphthalimide; Diphenyliodonium hexafluorophosphate, (4-methoxyphenyl)phenyliodonium trifluoromethanesulfonate, bis(p-tert-butylphenyl)iodonium trifluoromethanesulfonate, triphenyl sulfonate onium salts such as phonium hexafluorophosphate, (4-methoxyphenyl)diphenylsulfonium trifluoromethanesulfonate, and (p-tert-butylphenyl)diphenylsulfonium trifluoromethanesulfonate; Benzoin tosylate, such as benzoin tosylate and α-methylbenzoin tosylate; Other examples include diphenyl iodonium salt, triphenyl sulfonium salt, phenyl diazonium salt, and benzyl carbonate.

In the positive photosensitive resin composition according to the present invention, the content of component (C) is not particularly limited as long as it does not impair the purpose of the present invention, and is preferably 0.1 to 15 parts by weight based on 100 parts by weight of component (A). , 1 to 10 parts by weight is more preferable.

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

The positive photosensitive resin composition of the present invention may further contain component (D). As a result, the resist pattern shape can easily be improved, for example, the verticality of the side walls is high, and a resist pattern with excellent sphericality can easily be obtained. Although the reason for this effect is not clear, it is presumed that it is because the tertiary aliphatic amine is uniformly dispersed in the resist film and can effectively suppress the diffusion of acid generated from component (C). Moreover, by containing component (D), the stability of the positive photosensitive resin composition over waiting time is also likely to be improved. (D) Component can be used individually or in combination of two or more types.

Since a wide variety of tertiary aliphatic amines have already been proposed, known ones may be used arbitrarily, for example, amines (triamines) in which all three hydrogen atoms of ammonia NH ₃ are substituted with alkyl groups or hydroxyalkyl groups having 12 or less carbon atoms. alkyl amine or tri(alkyl alcohol) amine).

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

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

One type of tertiary aliphatic amine may be used individually, or two or more types may be used together.

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

There is no particular limitation on nitrogen-containing organic compounds other than tertiary aliphatic amines, and known compounds may be used arbitrarily. Specific examples include aliphatic amines other than cyclic amines and tertiary aliphatic amines.

Here, in the present invention, “aliphatic amine” means a chain-shaped amine that has a structure in which at least one of the three hydrogen atoms of ammonia NH ₃ is substituted with a monovalent aliphatic group and does not have a ring structure in the molecule. The aliphatic group preferably has 1 to 12 carbon atoms.

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

Examples of cyclic amines include heterocyclic compounds 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 aliphatic monocyclic amines include piperidine and piperazine.

The aliphatic polycyclic amine preferably has 6 to 10 carbon atoms, specifically 1,5-diazabicyclo[4.3.0]-5-nonene, 1,8-diazabicyclo[5.4.0]-7-unde. Examples include sen, hexamethylenetetramine, and 1,4-diazabicyclo[2.2.2]octane.

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

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

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

These may be used individually, or two or more types may be used in combination.

In the positive photosensitive resin composition according to the present invention, the content of component (D) is 0.005 to 5.0 parts by weight based on 100 parts by weight of component (A), since the effect of adding component (D) is easily obtained. It is preferable, 0.01 to 0.3 parts by weight is more preferable, and 0.015 to 0.2 parts by weight is even more preferable.

[Organic solvent (S)]

The positive photosensitive resin composition according to the present invention may contain an organic solvent (S). Since the positive photosensitive resin composition contains an organic solvent (S), it is easy to adjust the applicability 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's easy to break down. (S) Components can be used individually or in combination of two or more.

(S) Specific examples of the component include ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, and 2-heptanone; Ethylene glycol, ethylene glycol monoacetate, diethylene glycol, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, dipropylene glycol, and dipropylene glycol monoacetate, and their monomethyl ether, monoethyl ether, and monopropyl ether. polyhydric alcohols and derivatives thereof such as monobutyl ether, monophenyl ether (for example, propylene glycol monomethyl ether acetate); Cyclic ethers such as dioxane; Ethyl formate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl pyruvate, ethyl ethoxyacetate, methyl methoxypropionate, ethyl ethoxypropionate, 2-hydride. Methyl hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl esters such as acetate; Aromatic hydrocarbons such as toluene and xylene; etc. can be mentioned.

In the positive photosensitive resin composition according to the present invention, the content of the organic solvent (S) is preferably 50 to 3000 parts by weight, and more preferably 100 to 2000 parts by weight, based on 100 parts by weight of component (A). When the content is within the above range, the applicability 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 easily adjusted.

[Other ingredients]

The positive photosensitive resin composition according to the present invention may further contain a polyvinyl resin in order to improve the reversibility of the formed film. Specific examples of 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 These copolymers, etc. can be mentioned. Since the polyvinyl resin has a low glass transition point, it is preferably polyvinylmethyl ether.

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

The positive photosensitive resin composition according to the present invention may further contain a surfactant in order to improve applicability, anti-foaming properties, leveling properties, etc. Specific examples of surfactants include BM-1000, BM-1100 (all manufactured by BM Chemistry Co., Ltd.), Megapack F142D, Megapack F172, Megapack F173, Megapack F183 (all manufactured by Dainippon Ink Chemicals Co., Ltd.), and Flurad FC-135. , Flurad FC-170C, Flurad FC-430, Flurad FC-431 (all manufactured by Sumitomo 3M), Sulfon S-112, Sulfon S-113, Sulfon S-131, Sulfon S-141, Commercially available fluorine-based surfactants such as Sulflon S-145 (all manufactured by Asahi Glass Co., Ltd.), SH-28PA, SH-190, SH-193, SZ-6032, and SF-8428 (all manufactured by Toray Silicone Co., Ltd.), etc. However, it is not limited to these.

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

Specific examples of acids and acid anhydrides include monocarboxylic acids such as acetic acid, propionic acid, n-butyric acid, isobutyric acid, n-valeric acid, isovaleric acid, benzoic acid, and cinnamic acid; Lactic acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, salicylic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 2-hydroxycinnamic acid, 3-hydroxycinnamic acid, 4-hydroxycinnamic acid, 5 -Hydroxymonocarboxylic acids such as hydroxyisophthalic acid and syringic 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, butane. Polyhydric carboxylic acids such as tetracarboxylic acid, trimellitic acid, pyromellitic acid, cyclopentanetetracarboxylic acid, butanetetracarboxylic acid, and 1,2,5,8-naphthalenetetracarboxylic acid; Itaconic acid anhydride, succinic anhydride, citraconic acid anhydride, dodecenylsuccinic anhydride, tricarbanilic anhydride, maleic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hymic acid anhydride, 1,2,3,4-butane. Acid anhydrides such as tetracarboxylic acid anhydride, cyclopentanetetracarboxylic dianhydride, phthalic acid anhydride, pyromellitic anhydride, trimellitic acid anhydride, benzophenone tetracarboxylic acid anhydride, ethylene glycol bis trimellitate anhydride, and glycerin tris trimellitate anhydride; etc. can be mentioned.

<Method for producing 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 can be prepared by mixing and stirring each of the above components in a conventional manner, and if necessary, dispersed and stirred using a disperser such as a dissolver, homogenizer, or 3-roll mill. Mixing may be performed. Additionally, after mixing, it may be additionally filtered using a mesh or membrane filter.

<Method of manufacturing micro lens pattern>

The method for manufacturing a micro lens pattern according to the present invention includes a positive photosensitive resin composition layer forming step of forming a positive photosensitive resin composition layer using the positive photosensitive resin composition according to the present invention, and selectively forming the positive photosensitive resin composition layer. It includes an exposure process of exposing to light, a development process of developing the exposed positive photosensitive resin composition layer, and a heating process of heating the positive photosensitive resin composition layer after development.

[Positive photosensitive resin composition layer formation process]

In the positive photosensitive resin composition layer forming step, a 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. Examples of the base material include a lens material layer described later.

The method of forming the positive 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 a high-viscosity gel, for example, a predetermined amount of the positive photosensitive resin composition is supplied onto a substrate, and then the positive photosensitive resin composition is pressed while appropriately heating the positive photosensitive resin composition. Layers can be formed. When the positive photosensitive resin composition is a liquid (for example, when the positive photosensitive resin composition contains an organic solvent (S)), contact transfer type application using, for example, a roll coater, reverse coater, bar coater, or slit coater. Apply the positive photosensitive resin composition to the desired film thickness on the substrate using a non-contact coating device such as a spinner (rotary coating device) or curtain flow coater to form a coating film, followed by appropriate heat treatment (prebake (post)). By removing the organic solvent in the coating film through apply bake (PAB) treatment, a positive photosensitive resin composition layer can be formed.

The conditions of the heat treatment vary depending on the type, mixing ratio, coating film thickness, etc. of each component in the composition, but the heating temperature is, for example, 60 to 150°C (preferably 70 to 140°C), and the heating time is, For example, about 0.5 to 60 minutes (preferably 1 to 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 in the range of 400 nm to 2.0 μm.

[Exposure process]

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

After exposure, PEB treatment (post-exposure heat treatment) is appropriately performed. The conditions for PEB treatment vary depending on the type, mixing ratio, coating film thickness, etc. of each component in the composition, but for example, the heating temperature is 60 to 150°C (preferably 70 to 140°C), and the heating time is, for example, For example, it is about 0.5 to 60 minutes (preferably 1 to 50 minutes).

[Development process]

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

Examples of developing solutions include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, and methyldiethylamine. , dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo[5.4.0]-7-undecene, 1,5- An aqueous solution of an alkali such as diazabicyclo[4.3.0]-5-nonane can be used. Additionally, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the aqueous solution of the above-mentioned alkalis can also be used as a developing solution. As a developing solution, a 0.1 to 10% by weight aqueous solution of tetramethylammonium hydroxide is preferable.

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

After development, properly wash under running water for 30 to 90 seconds and dry using an air gun or oven.

[Heating process]

In the heating process, the positive photosensitive resin composition layer after development is heated. As a result, the positive photosensitive resin composition layer is thermally deformed, thereby forming a micro lens pattern, preferably a micro lens pattern on a convex surface.

The heating conditions vary depending on the type, mixing ratio, coating film thickness, etc. of each component in the composition, but for example, the heating temperature is 130 to 170°C (preferably 140 to 160°C), and the heating time is, for example, It lasts about 1 to 30 minutes (preferably 3 to 10 minutes).

<Method for manufacturing micro lenses>

The method for manufacturing a micro lens pattern according to the present invention includes a positive photosensitive resin composition layer laminating process of laminating a positive photosensitive resin composition layer using the positive photosensitive resin composition according to the present invention on a lens material layer, and the positive photosensitive resin composition An exposure process of selectively exposing the composition layer, a development process of developing the exposed positive photosensitive resin composition layer, and heating the positive photosensitive resin composition layer after development to form a mask layer having a micro lens pattern. It includes a mask layer forming step, 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.

[Positive photosensitive resin composition layer lamination process]

In the positive photosensitive resin composition layer lamination process, a 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, a conventionally known one can be used. For example, a transparent planarization film alone or an anti-reflection film and a transparent planarization film are provided on a substrate such as a silicon wafer on which an image element is formed, and a lens material layer provided on the transparent planarization film is included. You can.

The positive photosensitive resin composition layer lamination process is the same as the positive photosensitive resin composition layer forming process in the above-described micro lens pattern manufacturing method, except that a lens material layer is used as a base material.

[Exposure process]

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

[Development process]

In the development process, the exposed positive photosensitive resin composition layer is developed. The developing process is the same as the developing process in the above-described micro lens pattern manufacturing method.

[Mask layer formation process]

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

[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. Thereby, a micro lens can be obtained from the lens material layer.

Dry etching is not particularly limited, and examples include dry etching using plasma (oxygen, argon, CF ₄ , etc.), corona discharge, etc.

[ 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]

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

In each of the following formulas representing A-1 to A-4 below, the subscripts (x, y, and z) attached to each repeating unit are the ratio (mol%) of each repeating unit to the total repeating units included in the resin. am.

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

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

[Tuesday 23]

A-2: Resin represented by the formula below (weight average molecular weight 8000, x=75, y=25)

[Tuesday 24]

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

[Tuesday 25]

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

[Tuesday 26]

B-1: Compound represented by the formula below

[Tuesday 27]

C-1: Compound represented by the formula below

[Tuesday 28]

C-2: Compound represented by the formula below

[Tuesday 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 limiting resolution)]

The positive photosensitive resin composition prepared in Examples or Comparative Examples was applied using a spinner onto a Si substrate on which an antireflection film and an acrylic transparent planarization film were formed, thereby forming a coating film. The coating film was prebaked on a hot plate at 100°C for 90 seconds and dried to form a positive photosensitive resin composition layer with a thickness of 800 nm.

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

Thereafter, the positive photosensitive resin composition layer was subjected to PEB treatment at 110°C for 90 seconds, then developed with a 2.38% by weight tetramethylammonium hydroxide aqueous solution at 23°C for 60 seconds, and then Afterwards, rinse was performed for 30 seconds using pure water. Pure water was shaken off and dried to obtain a resist pattern.

The cross section of the obtained resist pattern was observed with SEM. The limit resolution was obtained by changing the mask dimensions, and the limit resolution was evaluated based on the following criteria. The results are shown in Table 2.

◎ (Very good): Limiting resolution is 0.17㎛ or less.

○ (Good): Limit resolution is greater than 0.17㎛ and less than 0.18㎛

△ (defect): Limit resolution exceeds 0.18㎛ and is less than 0.19㎛

× (Very poor): Limit resolution exceeds 0.19㎛

[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 based on the following criteria. The results are shown in Table 2. A white band is confirmed when the dimension of the bottom portion of the resist pattern is larger than the dimension of the upper portion. The width of the white band is the difference in dimensions between the upper and lower surfaces and indicates the degree of taper shape. The smaller the width of the white band, the higher and better the verticality of the pattern.

◎ (Very good): White band width is less than 0.07㎛

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

△ (defect): White band width is 0.075㎛ or more and less than 0.08㎛

× (very poor): White band width is 0.08㎛ or more

[Evaluation of flow performance (flow margin)]

The resist pattern obtained in the same manner as above was post-baked at each temperature of 130 to 170°C for 300 seconds, and the cross section of the resist pattern was observed with an SEM. Through the above post-bake process, the minimum temperature T ₁ at which a micro lens pattern is formed and the minimum temperature T ₂ at which the lower portions of adjacent micro lens patterns contact each other were determined. The difference T ₂ -T ₁ was used as the flow margin and evaluated according to the following criteria. The results are shown in Table 2.

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

◎ (Good): Flow margin is above 7℃ and below 10℃

○ (Slightly good): Flow margin is above 4℃ and below 7℃.

× (defect): Flow margin is less than 4℃

As can be seen from Table 2, the compositions of Examples 1 to 7 containing component (A) and component (B) of the present invention had both excellent resolution and wide flow margin. In comparison, the compositions of Comparative Examples 1 to 3 that did not contain component (A) and/or component (B) of the present invention had narrow flow margins.

Claims (9)

A resin (A) having an acid-dissociable, dissolution-inhibiting group and increasing solubility in alkali by the action of an acid, a compound (B) having at least two vinyloxy groups, and iron containing a photoacid generator (C). ) A positive photosensitive resin composition for manufacturing a micro-lens pattern on a surface,
The resin (A) includes a structural unit (a1) derived from hydroxystyrene, and a structural unit (a2) in which the hydrogen atom of at least one hydroxyl group in the structural unit derived from hydroxystyrene is replaced with an acid-dissociable, dissolution-inhibiting group-containing group. The branches contain resin (A1),
The micro-lens pattern on the convex surface is,
A positive photosensitive resin composition layer forming process of forming a positive photosensitive resin composition layer using the positive photosensitive resin composition;
an exposure process of selectively exposing the positive photosensitive resin composition layer;
A development process of developing the exposed positive photosensitive resin composition layer;
A positive photosensitive resin composition manufactured by a method for producing a micro lens pattern, comprising a heating step of forming a convex surface-like micro lens pattern by heating and deforming the positive photosensitive resin composition layer after development. In claim 1,
A positive photosensitive resin composition wherein the resin (A1) has a weight average molecular weight of 5000 to 30000. In claim 1,
The resin (A1) is a positive photosensitive resin composition containing a structural unit represented by the following formula (a1-1) and a resin (A2) having a structural unit represented by the following formula (a2-1).

(In the formula, 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, q, s, and t independently represent integers from 0 to 4, provided that p+q and r+s+t independently represent integers from 1 to 5. am) In claim 3,
The resin (A2) is a resin (A3) having a structural unit represented by the formula (a1-1), a structural unit represented by the formula (a2-2), and/or a structural unit represented by the formula (a2-3). A positive photosensitive resin composition comprising a.

(Wherein, R ^a3 , R ^a5 , r, s, and t are the same as 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 combine with each other to form a ring) In claim 4,
The resin (A3) is a resin (A4) having a structural unit represented by the formula (a1-1), a structural unit represented by the formula (a2-2), and/or a structural unit represented by the formula (a1-1). A positive photosensitive resin composition containing a resin (A5) having a structural unit represented by the formula (a2-3). In claim 5,
A positive type photosensitive resin composition wherein the amount of the resin (A4) is 60 to 90 mol% relative to the total of the resin (A4) and the resin (A5). In claim 1,
A positive photosensitive resin composition further containing 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 any one of claims 1 to 7,
an exposure process of selectively exposing the positive photosensitive resin composition layer;
A development process of developing the exposed positive photosensitive resin composition layer;
A method for manufacturing a micro lens pattern, comprising a heating step of forming a convex-shaped micro lens pattern by heating and deforming the positive photosensitive resin composition layer after development. A positive photosensitive resin composition layer laminating process of laminating a positive photosensitive resin composition layer using the positive photosensitive resin composition of any one of claims 1 to 7 on a lens material layer;
an exposure process of selectively exposing the positive photosensitive resin composition layer;
A development process of developing the exposed positive photosensitive resin composition layer;
A mask layer forming step of forming a mask layer having a convex microlens pattern by heating and deforming the developed positive photosensitive resin composition layer;
A method of manufacturing a micro lens including 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.