JP5753434B2 - Chemical amplification type positive photosensitive composition, method for forming cured film, cured film - Google Patents

Description

  The present invention relates to a chemically amplified positive photosensitive composition in which the toughness of a cured film is improved, a method for forming a cured film, a cured film, and a device including a rewiring layer using the same.

In recent years, in the semiconductor field, devices have been highly integrated and increased in size, and the acceptance of thinner and smaller encapsulating resin packages has increased, and there has been a strong demand for cost reduction of semiconductor packages. On the other hand, surface mounting methods such as WL-CSP (wafer level chip size package) using a rewiring layer have recently been proposed and are being adopted (Patent Documents 1 and 2).
In WL-SCP using a rewiring layer, a protective layer and an insulating layer are provided above and below with the rewiring layer sandwiched between them in order to protect the rewiring layer and ensure insulation. As a material for the protective layer / insulating layer, polyimide resin, polybenzoxazole resin, and the like are widely used. In this case, if a photosensitive polyimide or photosensitive polybenzthiazole resin imparted with photosensitive characteristics is used for the resin itself, the pattern creation process can be simplified and the manufacturing process can be shortened.

Japanese Patent Laid-Open No. 10-186664 JP 2001-194791 A

However, various resist materials mainly composed of polyimide resin and polybenzoxazole resin conventionally used as a rewiring layer are excellent in heat resistance and toughness, but require a high temperature for curing (usually 350 ° C. The above may cause damage to the already formed layer.
In Patent Document 1, by using a heat-resistant material precursor such as polyimide or polybenzoxazole having both a group that exhibits acidity and irradiation with actinic rays and a phenolic hydroxyl group, storage stability and developability in a solution state, Although there is a description that a positive photosensitive resin material having excellent cured film characteristics can be obtained, the sensitivity is low at an appropriate exposure amount of 300 mj / cm ² or more, and post-exposure post-exposure for obtaining desired cured film physical properties. A high temperature of 400 ° C. is also necessary.
Moreover, in patent document 2, it exposes by adding the acid-decomposable group which the solubility with respect to alkaline aqueous solution increases with a specific acid-catalyzed reaction with respect to the compound which generate | occur | produces an acid with a polyimide precursor or a polyoxazole precursor, and light. Although there is a description that a positive photosensitive resin material with high sensitivity and high resolving power is obtained, the sensitivity is still low with an appropriate exposure amount of 400 mj / cm ² or more, and after exposure for obtaining desired cured film properties. The post baking temperature also required a high temperature of 350 ° C.
An object of the present invention is to provide a photosensitive resin composition that can provide highly reliable electronic components with high sensitivity and process efficiency, low curing temperature, low damage to devices, and high reliability. Is to provide.
Moreover, the further subject of this invention is providing the semiconductor electronic component which comprised the cured film using the photosensitive resin composition of this invention, its manufacturing method, and this cured film.
The present invention aims to solve the above-mentioned problems, and aims to provide a material having high sensitivity, low temperature curing, sufficient heat resistance, and tough film quality. .

  Based on the above problems, the inventor of the present application has intensively studied, and as a result, a highly sensitive, highly transparent, low temperature curable chemically amplified positive photosensitive composition employs an epoxy resin having a specific structure as a crosslinking agent. As a result, it was found that the toughness necessary for the rewiring material can be imparted while maintaining the heat resistance, and the present invention has been completed. Specifically, the problems of the present invention were solved by the following means.

(1) (A) a compound that increases alkali solubility with acid, (B) a compound that generates acid upon irradiation with actinic rays and / or radiation, (C) a crosslinking agent, and (C) the crosslinking agent is represented by the following formula ( A chemically amplified positive photosensitive composition represented by I) having a number average molecular weight of 600 to 2,000.
Formula (I)
(In formula (I), A is composed of —O— and a divalent organic group, and includes at least a partial structure represented by the following formula (I-2).)
Formula (I-2)
(X represents a divalent organic group.)
(2) (A) a compound that increases alkali solubility with acid, (B) a compound that generates acid upon irradiation with actinic rays and / or radiation, (C) a crosslinking agent, and (C) the crosslinking agent is represented by the following formula ( A chemically amplified positive photosensitive composition represented by II) or (III).
Formula (II)
(In the formula (II), Ar represents an aromatic hydrocarbon group, X represents a divalent organic group, and n is an integer of 1 to 20.)
Formula (III)
(In formula (III), R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and X and Y each independently represent a divalent organic group. N is an integer of 0 to 20. )
(3) The chemically amplified positive photosensitive composition according to (1) or (2), wherein the compound whose alkali solubility is increased by (A) acid is an acetal resin.
(4) The chemically amplified positive photosensitive composition according to any one of (1) to (3), wherein the compound that generates acid upon irradiation with actinic rays and / or radiation is an oxime sulfonate compound.
(5) X in the formula (II) is an ethyleneoxyethyl group, di (ethyleneoxy) ethyl group, tri (ethyleneoxy) ethyl group, tetra (ethyleneoxy) ethyl group, propyleneoxypropyl group, di (propyleneoxy) ) Propyl group, tri (propyleneoxy) propyl group, tetra (propyleneoxy) propyl group, butyleneoxybutyl group, di (butyleneoxy) butyl group, tri (butyleneoxy) butyl group, tetra (butyleneoxy) butyl group, carbon The chemical amplification type according to any one of (2) to (4), selected from an alkylene group having 2 to 15 atoms and an aliphatic hydrocarbon group having 6 to 17 carbon atoms having a cycloalkane skeleton. Positive photosensitive composition.
(6) The chemically amplified positive photosensitive composition according to any one of (2) to (5), wherein n in the formula (II) is 2 to 10.
(7) Any one of (2) to (5), wherein Ar in the formula (II) is a methylenediphenylene group, 2,2-propane-diphenyl group, or any one of the followings: The positive photosensitive material described in 1.
(8) X and Y in the formula (III) are each an ethyleneoxyethyl group, a di (ethyleneoxy) ethyl group, a tri (ethyleneoxy) ethyl group, a tetra (ethyleneoxy) ethyl group, a propyleneoxypropyl group, Di (propyleneoxy) propyl group, tri (propyleneoxy) propyl group, tetra (propyleneoxy) propyl group, butyleneoxybutyl group, di (butyleneoxy) butyl group, tri (butyleneoxy) butyl group, tetra (butyleneoxy) (2) to (4), which is selected from a butyl group, an alkylene group having 2 to 15 carbon atoms, and an aliphatic hydrocarbon group having 6 to 17 carbon atoms having a cycloalkane skeleton. A chemically amplified positive photosensitive composition.
(9) The chemically amplified positive photosensitive composition according to any one of (2) to (4) and (8), wherein n in the formula (III) is 1 to 10.
(10) The crosslinking agent according to any one of (1) to (9), comprising (C) a crosslinking agent in a proportion of 10 to 80 parts by weight relative to 100 parts by weight of the compound (A) whose alkali solubility increases with an acid. A chemically amplified positive photosensitive composition.
(11) The chemically amplified positive photosensitive composition according to any one of (1) to (10), which is used for forming a semiconductor rewiring.
(12) (1) A step of applying the chemically amplified positive photosensitive composition according to any one of (1) to (11) on a substrate,
(2) a step of removing the solvent from the applied chemically amplified positive photosensitive composition;
(3) a step of exposing the applied chemically amplified positive photosensitive composition with actinic rays;
(4) a step of developing the exposed chemically amplified positive photosensitive composition with an aqueous developer, and
(5) A step of thermally curing the developed chemically amplified positive photosensitive composition.
(13) A cured film formed by the method according to (12).

  According to the present invention, it has become possible to provide a material having high sensitivity, low temperature curing, sufficient heat resistance, and tough film quality.

FIG. 1 is a schematic cross-sectional view showing a wiring structure of a semiconductor device.

Hereinafter, the contents of the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
In the description of the group (atomic group) in this specification, the description which does not describe substitution and unsubstituted includes what has a substituent with what does not have a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
(Meth) acrylic acid means acrylic acid and / or methacrylic acid.
In the present specification, post-exposure baking after exposure may be referred to as PEB.

  The chemically amplified positive photosensitive composition of the present invention comprises (A) a compound whose alkali solubility is increased by an acid, (B) a compound which generates an acid upon irradiation with actinic rays and / or radiation, and a specific (C) crosslinking agent. It is characterized by including. The (C) crosslinking agent used in the present invention is an epoxy resin having a long distance between epoxy groups and a flexible structure. By employing such a cross-linking agent, it is possible to provide a chemically amplified positive photosensitive composition that maintains high sensitivity and high transparency, can be cured at low temperature, and forms a tough cured film. Furthermore, the present invention can provide such a material at a low cost. Hereinafter, the details of the chemically amplified positive photosensitive composition of the present invention will be described.

(A) Compound whose alkali solubility is increased by an acid In the present invention, the compound whose alkali solubility is increased by an acid is a resin which is alkali-insoluble or hardly soluble in alkali and becomes alkali-soluble when an acid-dissociable group is dissociated. Can be widely used.
Here, “alkali-soluble” in the present invention refers to a coating film (thickness) of the compound (resin) formed by applying a solution of the compound (resin) on a substrate and heating at 90 ° C. for 2 minutes. 3 μm) at 23 ° C. with a 0.4 mass% tetramethylammonium hydroxide aqueous solution. When the speed is 0.01 μm / second or more, it is considered that there is alkali solubility. On the other hand, “alkali insoluble” refers to a coating film (thickness 3 μm) of the compound (resin) formed by applying a solution of the compound (resin) on a substrate and heating at 90 ° C. for 2 minutes. The dissolution rate in a 0.4 mass% tetramethylammonium hydroxide aqueous solution at 23 ° C. is less than 0.01 μm / second, preferably less than 0.005 μm / second.

  (A) The compound that increases acid-alkali solubility is preferably an acetal resin, and may be referred to as an acetal resin having a structure represented by the following general formula (I) (hereinafter referred to as “(A) acetal resin”). ) Is more preferable.

R ¹ and R ² each independently represents a hydrogen atom, a linear or branched alkyl group or a cycloalkyl group. However, at least one of R ¹ and R ² represents an alkyl group or a cycloalkyl group.
R ³ represents a linear or branched alkyl group, a cycloalkyl group, or an aralkyl group.
R ¹ or R ² and R ³ may be linked to form a cyclic ether.

The alkyl group as R ¹ and R ^{2 in the} general formula (I) is preferably a linear or branched alkyl group having 1 to 6 carbon atoms. The cycloalkyl group as R ¹ and R ² is preferably a cycloalkyl group having 3 to 6 carbon atoms.
The alkyl group as R ³ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms. The cycloalkyl group as R ³ is preferably a cycloalkyl group having 3 to 10 carbon atoms.
The aralkyl group as R ³ is preferably an aralkyl group having 7 to 10 carbon atoms.
When R ¹ or R ² and R ³ are linked to form a cyclic ether, R ¹ or R ² and R ³ may be linked to form an alkylene chain having 2 to 5 carbon atoms. preferable.
The alkyl group, cycloalkyl group, and aralkyl group as R ³ may have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, and a halogen atom. 6 or less is preferable.

In the general formula (I), examples of R ⁷ in which R ¹ and one acetal ester structure of a carboxylic acid, a hydrogen atom of R ² (-COOR ^7), for example, 1-methoxyethyl group, 1-ethoxyethyl group 1-n-propoxyethyl group, 1-i-propoxyethyl group, 1-n-butoxyethyl group, 1-i-butoxyethyl group, 1-sec-butoxyethyl group, 1-t-butoxyethyl group, 1 -Cyclopentyloxyethyl group, 1-cyclohexyloxyethyl group, 1-norbornyloxyethyl group, 1-bornyloxyethyl, 1-benzyloxyethyl group, 1-phenethyloxyethyl group, (cyclohexyl) (methoxy) methyl Group, (cyclohexyl) (ethoxy) methyl group, (cyclohexyl) (n-propoxy) methyl group, (cyclohexyl Sil) (i-propoxy) methyl group, (cyclohexyl) (cyclohexyloxy) methyl group, (cyclohexyl) (benzyloxy) methyl group, (phenyl) (methoxy) methyl group, (phenyl) (ethoxy) methyl group, (phenyl) ) (N-propoxy) methyl group, (phenyl) (i-propoxy) methyl group, (phenyl) (cyclohexyloxy) methyl group, (phenyl) (benzyloxy) methyl group, (benzyl) (methoxy) methyl group, ( (Benzyl) (ethoxy) methyl group, (benzyl) (n-propoxy) methyl group, (benzyl) (i-propoxy) methyl group, (benzyl) (cyclohexyloxy) methyl group, (benzyl) (benzyloxy) methyl group, Examples include 2-tetrahydrofuranyl group and 2-tetrahydropyranyl group Door can be.

R ⁸ in the ketal ester structure of carboxylic acid (—COOR ⁸ ) in which neither R ¹ nor R ² in the general formula (I) is a hydrogen atom is, for example, a 1-methyl-1-methoxyethyl group, 1 -Methyl-1-ethoxyethyl group, 1-methyl-1-n-propoxyethyl group, 1-methyl-1-i-propoxyethyl group, 1-methyl-1-n-butoxyethyl group, 1-methyl-1 -I-butoxyethyl group, 1-methyl-1-sec-butoxyethyl group, 1-methyl-1-t-butoxyethyl group, 1-methyl-1-cyclopentyloxyethyl group, 1-methyl-1-cyclohexyloxy Ethyl, 1-methyl-1-norbornyloxyethyl, 1-methyl-1-bornyloxyethyl, 1-methyl-1-benzyloxyethyl, Til-1-phenethyloxyethyl group, 1-cyclohexyl-1-methoxyethyl group, 1-cyclohexyl-1-ethoxyethyl group, 1-cyclohexyl-1-n-propoxyethyl group, 1-cyclohexyl-1-i-propoxy Ethyl group, 1-cyclohexyl-1-cyclohexyloxyethyl group, 1-cyclohexyl-1-benzyloxyethyl group, 1-phenyl-1-methoxyethyl group, 1-phenyl-1-ethoxyethyl group, 1-phenyl-1 -N-propoxyethyl group, 1-phenyl-1-i-propoxyethyl group, 1-phenyl-1-cyclohexyloxyethyl group, 1-phenyl-1-benzyloxyethyl group, 1-benzyl-1-methoxyethyl group 1-benzyl-1-ethoxyethyl group, 1-benzyl-1-n-propo Siethyl group, 1-benzyl-1-i-propoxyethyl group, 1-benzyl-1-cyclohexyloxyethyl group, 1-benzyl-1-benzyloxyethyl group, 2-methyl-2-tetrahydrofuranyl group, 2-methyl- A 2-tetrahydropyranyl group, 1-methoxycyclopentyl group, 1-methoxy-cyclohexyl group and the like can be mentioned.

In the acetal structure or ketal structure of the carboxylic acid, an acetal structure is more preferable from the viewpoint of process stability. Preferable R ⁷ in the acetal ester structure (—COOR ⁷ ) of carboxylic acid is preferably a 1-ethoxyethyl group, a 1-cyclohexyloxyethyl group, a 2-tetrahydrofuranyl group, or a 2-tetrahydropyranyl group, from the viewpoint of sensitivity. A 1-ethoxyethyl group and a 1-cyclohexyloxyethyl group are particularly preferable.

(A) The acetal resin is preferably an acrylic polymer.
The “acrylic polymer” in the present invention is an addition polymerization type resin, is a polymer containing a structural unit derived from (meth) acrylic acid or an ester thereof, and is derived from (meth) acrylic acid or an ester thereof. You may have structural units other than a structural unit, for example, the structural unit derived from styrene, the structural unit derived from a vinyl compound, etc. Moreover, you may include both the structural units derived from (meth) acrylic acid and its ester.
In the (A) acetal resin, the structural unit derived from (meth) acrylic acid or an ester thereof is preferably 50 mol% or more with respect to all structural units in the (A) acetal resin, and is 80 mol%. The above is more preferable, and a polymer composed of only a structural unit derived from (meth) acrylic acid or an ester thereof is particularly preferable.

  (A) In the acetal resin, the content of the structural unit represented by the general formula (1) is preferably 10 to 100 mol%, more preferably 20 to 90 mol%, and particularly preferably 30 to 80 mol%. 40 mol% or less is preferable, as for the content rate of the structural unit containing a carboxyl group, 5-25 mol% is more preferable, and 10-20 mol% is especially preferable.

The (A) acetal resin used in the present invention further includes a structural unit (a1) having a structure that generates a carboxy group with an acid, a structural unit (a2) having a carboxy group or a phenolic hydroxyl group, and a hydroxyl group or alkyleneoxy. It is preferable to contain at least one kind of the structural unit (a4) having a group, and it is more preferable that the resin contains all of them. Furthermore, the acetal resin used in the present invention may contain a structural unit (a3) and a structural unit (a5) having an epoxy group or an oxetanyl group.
The (A) acetal resin is preferably a resin that is alkali-insoluble and becomes alkali-soluble when the acid-decomposable group in the structural unit (a1) having a structure that generates a carboxy group with an acid is decomposed.

<Structural unit (a1) having a structure generating a carboxy group with an acid>
The (A) acetal resin in the present invention contains a structural unit (a1) having a structure that generates a carboxy group with an acid (hereinafter, appropriately referred to as “structural unit (a1)”). The structural unit (a1) contains a structure in which a carboxy group is protected.
As the compound used for forming the structural unit (a1), any compound can be used as long as it can be a compound used for forming the structural unit (a1) by protecting the carboxy group. Examples of the compound having a carboxy group include monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, and α-methyl-p-carboxystyrene; dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid. Examples of the acid include acrylic acid and methacrylic acid. Moreover, as a structural unit (a1), the structural unit derived from the carboxylic acid by which these carboxy groups were protected can be mentioned as a preferable thing.

  Preferable specific examples of the radical polymerizable monomer used for forming the structural unit (a1) include, for example, 1-ethoxyethyl methacrylate, 1-ethoxyethyl acrylate, 1-methoxyethyl methacrylate, 1-methoxyethyl acrylate. 1-n-butoxyethyl methacrylate, 1-n-butoxyethyl acrylate, 1-isobutoxyethyl methacrylate, 1-i-butoxyethyl acrylate, 1- (2-ethylhexyloxy) ethyl methacrylate, 1- (2-ethylhexyloxy) ) Ethyl acrylate, 1-n-propoxyethyl methacrylate, 1-n-propoxyethyl acrylate, 1-cyclohexyloxyethyl methacrylate, 1-cyclohexyloxyethyl acrylate, 1- (2-cyclo Xylethoxy) ethyl methacrylate, 1- (2-cyclohexylethoxy) ethyl acrylate, 1-benzyloxyethyl methacrylate, 1-benzyloxyethyl acrylate, tetrahydro-2H-pyran-2-yl methacrylate, tetrahydro-2H-pyran acrylate -2-yl, tetrahydrofuran-2-yl methacrylate, tetrahydrofuran-2-yl acrylate, and the like. Particularly preferred are 1-ethoxyethyl methacrylate, 1-ethoxyethyl acrylate, tetrahydrofuran-2 methacrylate. -Yl, tetrahydrofuran-2-yl acrylate, 1-cyclohexyloxyethyl methacrylate, and 1-cyclohexyloxyethyl acrylate. These structural units (a1) can be used individually by 1 type or in combination of 2 or more types.

  As the radical polymerizable monomer used for forming the structural unit (a1), a commercially available one may be used, or one synthesized by a known method may be used. For example, the monomer represented by the following formula (II) can be synthesized by reacting (meth) acrylic acid with a vinyl ether compound in the presence of an acid catalyst as shown below.

In formula (II), R ⁶ represents a hydrogen atom or a methyl group, R ⁵ has the same meaning as R ³ in formula (I).

  The structural unit (a1) can also be formed by reacting the carboxy group with a vinyl ether compound after polymerizing the protected carboxy group with the structural units (a2) to (a5) and precursors thereof described later. it can. In addition, the specific example of the preferable structural unit formed in this way is the same as the structural unit derived from the preferable specific example of the said radical polymerizable monomer.

  Preferable specific examples of the structural unit (a1) include the following structural units (a1-1) to (a1-8). Among these, structural units represented by (a1-1) to (a1-4), (a1-7) and (a1-8) are particularly preferable.

  In all the structural units constituting the acetal resin, the content of the structural unit (a1) is 20 to 60 mol%, more preferably 25 to 60 mol%, and particularly preferably 25 to 55 mol%. By containing the structural unit (a1) at the above ratio, a highly sensitive chemically amplified positive photosensitive composition can be obtained.

<Structural unit (a2) having carboxy group or phenolic hydroxyl group>
(A) The acetal resin contains a structural unit (a2) having a carboxy group or a phenolic hydroxyl group (hereinafter referred to as “structural unit (a2)” as appropriate).
Examples of the structural unit (a2-1) having a carboxy group include unsaturated carboxylic acids having at least one carboxy group in the molecule, such as unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, and unsaturated tricarboxylic acid. The structural unit derived from is mentioned.

As unsaturated carboxylic acid used in order to obtain the structural unit (a2-1) which has a carboxy group, what is illustrated below is used.
That is, examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid.
Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid.

  Moreover, the acid anhydride may be sufficient as unsaturated polyhydric carboxylic acid used in order to obtain the structural unit (a2-1) which has a carboxy group. Specific examples include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. The unsaturated polyvalent carboxylic acid may be a mono (2-methacryloyloxyalkyl) ester of a polyvalent carboxylic acid. For example, succinic acid mono (2-acryloyloxyethyl), succinic acid mono (2 -Methacryloyloxyethyl), mono (2-acryloyloxyethyl) phthalate, mono (2-methacryloyloxyethyl) phthalate and the like.

  Further, the unsaturated polyvalent carboxylic acid may be a mono (meth) acrylate of the dicarboxy polymer at both ends, and examples thereof include ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate.

  As the unsaturated carboxylic acid, acrylic acid-2-carboxyethyl ester, methacrylic acid-2-carboxyethyl ester, maleic acid monoalkyl ester, fumaric acid monoalkyl ester, 4-carboxystyrene and the like can also be used.

  Among these, from the viewpoint of developability, it is preferable to use acrylic acid or methacrylic acid to form the structural unit (a2-1) having a carboxy group.

The structural unit (a2-1) having a carboxy group can also be obtained by reacting a structural unit having a hydroxyl group with an acid anhydride.
As the acid anhydride, known ones can be used. Specific examples include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and chlorendic anhydride. Examples include basic acid anhydrides; acid anhydrides such as trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic acid anhydride, and biphenyl tetracarboxylic acid anhydride. Among these, phthalic anhydride, tetrahydrophthalic anhydride, or succinic anhydride is preferable from the viewpoint of developability.

  Examples of the radical polymerizable monomer used to form the structural unit (a2-2) having a phenolic hydroxyl group include hydroxystyrenes such as p-hydroxystyrene and α-methyl-p-hydroxystyrene, Compounds described in paragraphs [0011] to [0016] of Kokai 2008-40183, 4-hydroxybenzoic acid derivatives described in paragraphs [0007] to [0010] of Japanese Patent No. 2888454, 4-hydroxybenzoic acid Preferred examples include an addition reaction product of glycidyl methacrylate and 4-hydroxybenzoic acid and glycidyl acrylate.

  Among the radically polymerizable monomers used to form the structural unit (a2), methacrylic acid, acrylic acid, compounds described in paragraphs 0011 to 0016 of JP2008-40183A, and Japanese Patent No. 2888454 More preferred are 4-hydroxybenzoic acid derivatives according to paragraphs 0007 to 0010, an addition reaction product of 4-hydroxybenzoic acid and glycidyl methacrylate, and an addition reaction product of 4-hydroxybenzoic acid and glycidyl acrylate. From the viewpoint of properties, methacrylic acid and acrylic acid are particularly preferable. These structural units can be used singly or in combination of two or more.

  The structural unit (a2) is preferably introduced in such a range that the (A) acetal resin does not become alkali-soluble. In all structural units constituting the (A) acetal resin, the content of the structural unit (a2) is 2 to 20 mol%, more preferably 2 to 15 mol%, and particularly preferably 3 to 15 mol%. . By containing the structural unit (a2) at the above ratio, high sensitivity can be obtained and developability can be improved. In particular, by using a structural unit (a4) and a structural unit (a2) described later in combination, very high sensitivity can be obtained.

<Structural unit (a3) having epoxy group and / or oxetanyl group>
(A) The acetal resin contains a structural unit (a3) having an epoxy group or an oxetanyl group (hereinafter, appropriately referred to as “structural unit (a3)”). Both structural units having an epoxy group and an oxetanyl group may be included.
The group having an epoxy group is not particularly limited as long as it has an epoxy ring, but a glycidyl group and a 3,4-epoxycyclohexylmethyl group can be preferably exemplified.
The group having an oxetanyl group is not particularly limited as long as it has an oxetane ring, but a (3-ethyloxetane-3-yl) methyl group can be preferably exemplified.
The structural unit (a3) only needs to have at least one epoxy group or oxetanyl group in one structural unit, one or more epoxy groups and one or more oxetanyl groups, two or more epoxy groups, or Although it may have two or more oxetanyl groups and is not particularly limited, it preferably has a total of 1 to 3 epoxy groups and / or oxetanyl groups, and a total of 1 or 2 epoxy groups and / or oxetanyl groups It is more preferable to have one epoxy group or oxetanyl group.

  Specific examples of the radical polymerizable monomer used to form the structural unit having an epoxy group include, for example, glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, and glycidyl α-n-propyl acrylate. Glycidyl α-n-butyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, acrylate-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, described in paragraphs [0031] to [0035] of Japanese Patent No. 4168443 Compounds containing alicyclic epoxy skeletons And the like.

  Examples of the radical polymerizable monomer used to form a structural unit having an oxetanyl group include, for example, an oxetanyl group described in paragraphs [0011] to [0016] of JP-A No. 2001-330953 ( And (meth) acrylic acid esters.

  (A3) As an example of the radical polymerizable monomer used for forming the structural unit, a monomer containing a methacrylic ester structure and a monomer containing an acrylic ester structure are preferable.

Among these monomers, more preferred are glycidyl methacrylate, glycidyl acrylate, compounds containing an alicyclic epoxy skeleton described in paragraphs [0034] to [0035] of Japanese Patent No. 4168443, and It is a (meth) acrylic acid ester having an oxetanyl group described in paragraphs [0011] to [0016] of JP 2001-330953 A.
Particularly preferred from the viewpoint of heat-resistant transparency is a structural unit derived from either (3-ethyloxetane-3-yl) methyl acrylate or methyl (3-ethyloxetane-3-yl) methacrylate. is there.
These structural units (a3) can be used individually by 1 type or in combination of 2 or more types.

  Preferable specific examples of the structural unit (a3) include the following structural units.

  Among all the structural units constituting the (A) acetal resin, the content of the structural unit (a3) is 20 to 55 mol%, more preferably 25 to 55 mol%, particularly preferably 25 to 50 mol%. By containing the structural unit (a3) at the above ratio, the physical properties of the cured film are improved.

<Structural unit (a4) having hydroxyl group or alkyleneoxy group>
The (A) acetal resin contains a structural unit (a4) having a hydroxyl group or an alkyleneoxy group (hereinafter, appropriately referred to as “structural unit (a4)”). Both structural units having a hydroxyl group and an alkyleneoxy group may be included.
The hydroxyl group in the structural unit (a4) refers to a hydroxyl group other than the phenolic hydroxyl group. When the structural units (a1) to (a3) have a hydroxyl group, the structural units (a1) to (a3) are used instead of the structural unit (a4).
As the structural unit (a4), any structural unit having a hydroxyl group and / or an alkyleneoxy group can be used, and preferred examples include a hydroxyl group-containing (meth) acrylate ester, an alkyl group-terminated polyester. Examples include structural units derived from (meth) acrylic acid esters of alkylene glycol and (meth) acrylic acid esters of aryl-terminated polyalkylene glycol.

  Examples of the hydroxyl group-containing (meth) acrylic acid ester include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and (meth) acrylic acid 2,3. -Hydroxyalkyl esters of (meth) acrylic acid such as dihydroxypropyl, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, poly (ethylene glycol / propylene glycol)- Mono (meth) acrylate, polyethylene glycol / polypropylene glycol-mono (meth) acrylate, poly (ethylene glycol / tetramethylene glycol) -mono (meth) acrylate, poly (propylene glycol) Tetraethylene glycol) - mono (meth) acrylate, propylene glycol polybutylene glycol - it may be mentioned as preferred examples of the mono (meth) acrylate.

Examples of (meth) acrylic acid esters of alkyl group-terminated polyalkylene glycols include methoxypolyethylene glycol- (meth) acrylate, octoxypolyethyleneglycol-polypropyleneglycol- (meth) acrylate, lauroxypolyethyleneglycol- (meth) acrylate, and steer. Roxypolyethylene glycol- (meth) acrylate can be mentioned as a preferred example.
Examples of the (meth) acrylic acid ester of the aryl group-terminated polyalkylene glycol include, for example, phenoxy polyethylene glycol- (meth) acrylate, phenoxy polyethylene glycol-polypropylene glycol- (meth) acrylate, nonylphenoxy-polyethylene glycol- (meth) acrylate, and nonyl. Preferable examples include phenoxy-polypropylene glycol- (meth) acrylate and nonylphenoxy-poly (ethylene glycol-propylene glycol)-(meth) acrylate.
Commercially available hydroxyl group-containing (meth) acrylic acid esters, alkyl group-terminated polyalkylene glycol (meth) acrylic acid esters and aryl group-terminated polyalkylene glycol (meth) acrylic acid esters can be used. Representative examples are Blemmer E, Blemmer PE-90, Blemmer PE-200, Blemmer PE-350, Blemmer P, Blemmer PP-1000, Blemmer PP-500, Blemmer PP-800, Blemmer 50 PEP-300, Blemmer 70 PEP- 350B, Blemmer 55PET-800, Blemmer PPT series, Blemmer 10PPB-500B, Blemmer AE-90, Blemmer AE-200, Blemmer AE-400, Blemmer AP-150, Blemmer AP-400, Blemmer AP-550, Blemmer PME-100 , Blemmer PME-200, Blemmer PME-400, Blemmer PME-1000, Blemmer 50POEP-800B, Blemmer PLE-200, Blemmer PSE-4 0, Blemmer PSE-1300, Blemmer PAE-50, Blemmer PAE-100, Blemmer 43PAPE-600B, Blemmer AME-400, Blemmer ALE series, Blemmer ANP-300, Blemmer 75ANP-600, Blemmer AAE-50, Blemmer AAE-300 (Above, manufactured by NOF Corporation).

In the structural unit (a4), the number of hydroxyl groups is preferably 1 to 10, more preferably 1 to 5, and most preferably 1 to 3. Moreover, as the number of repeating units of an alkyleneoxy group, 1-25 are preferable, 1-15 are more preferable, and 1-10 are the most preferable.
Preferred specific structures of the structural unit (a4) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, (meth) acrylic acid 2 , 3-dihydroxypropyl, methoxypolyethylene glycol- (meth) acrylate having 2 to 10 ethylene glycol repeating units, methoxypolypropylene glycol- (meth) acrylate having 2 to 10 propylene glycol repeating units, ethylene glycol repeating units and propylene 2-10 methoxypolyethylene glycol-polypropylene glycol- (meth) acrylate with a total of glycol repeating units, 2-10 with a sum of ethylene glycol repeating units and propylene glycol repeating units. Toxipolyethylene glycol-polypropylene glycol- (meth) acrylate, polyethylene glycol mono (meth) acrylate having 2 to 10 ethylene glycol repeating units, polypropylene glycol mono (meth) acrylate having 2 to 10 propylene glycol repeating units, ethylene glycol Poly (ethylene glycol / propylene glycol) -mono (meth) acrylate having 3 to 10 repeating units and propylene glycol repeating units, polyethylene glycol having 3 to 10 ethylene glycol repeating units and propylene glycol repeating units Polypropylene glycol-mono (meth) acrylate, etc., more preferably 2-hydroxyethyl (meth) acrylate, (meth) acrylic acid -Hydroxypropyl, 3-hydroxypropyl (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate having 2 to 10 ethylene glycol repeating units, and ethylene glycol repeating units; The sum of propylene glycol repeating units is 2-10 octoxypolyethylene glycol-polypropylene glycol- (meth) acrylate, most preferably methoxypolyethylene glycol- (meth) acrylate having 2-10 ethylene glycol repeating units and 2 -Hydroxyethyl (meth) acrylate.
A structural unit (a4) can be used individually by 1 type or in combination of 2 or more types.

(A) In all structural units constituting the acetal resin, the content of the structural unit (a4) is 0.5 to 30 mol%, more preferably 0.5 to 25 mol%, and 1 to 25 mol%. Particularly preferred.
Further, in all the structural units constituting the (A) acetal resin, the content of the structural unit (a4) is 3 to 30% by mass, more preferably 3 to 25% by mass, and particularly preferably 5 to 25% by mass. . By incorporating the structural unit (a4) at the above ratio, the developability is improved and a highly sensitive photosensitive composition can be obtained. In particular, by combining the structural unit (a2) and the structural unit (a4), a chemically amplified positive photosensitive composition with very high sensitivity can be obtained.

<Other structural unit (a5)>
(A) The acetal resin contains a structure other than the structural units (a1) to (a4) (hereinafter, appropriately referred to as “structural unit (a5)”) as long as the effects of the present invention are not hindered. Also good.
Examples of the radical polymerizable monomer used for forming the structural unit (a5) include compounds described in paragraphs [0021] to [0024] of JP-A No. 2004-264623 (provided that And excluding the structural units (a1) to (a4) described above.
Among these, (meth) acrylic acid esters having an alicyclic structure such as dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, and cyclohexyl acrylate are preferable from the viewpoint of improving electric characteristics. From the viewpoint of transparency, methyl (meth) acrylate is preferred.
A structural unit (a5) can be used individually by 1 type or in combination of 2 or more types.

  (A) The content rate of a structural unit (a5) is 0-40 mol% in all the structural units which comprise acetal type resin. When the (A) acetal resin includes the structural unit (a5), the content of the structural unit (a5) is preferably 1 to 40 mol% in all the structural units constituting the (A) acetal resin. 30 mol% is more preferable and 5-25 mol% is especially preferable.

In the present invention, the weight average molecular weight of the (A) acetal resin is preferably 1,000 to 50,000, more preferably 2,000 to 30,000, and most preferably 3,000 to 12. , 000.
In addition, the weight average molecular weight in this invention is a polystyrene conversion weight average molecular weight by gel permeation chromatography (GPC).

The method for introducing each structural unit contained in the (A) acetal resin used in the present invention may be a polymerization method or a polymer reaction method.
In the polymerization method, monomers containing a predetermined functional group are synthesized in advance, and then these monomers are copolymerized. That is, a radical comprising a structural unit (a1), a structural unit (a2), a structural unit (a3), a structural unit (a4), and a radical polymerizable monomer used to form the structural unit (a5) if necessary. It can be synthesized by polymerizing the polymerizable monomer mixture in an organic solvent using a radical polymerization initiator.
In the polymer reaction method, after a polymerization reaction is performed, a necessary functional group is introduced into the structural unit using a reactive group contained in the structural unit of the obtained copolymer.
Introduction of the structural units (a1) to (a5) into the (A) acetal resin may be carried out by a polymerization method or a polymer reaction method, or these two methods may be used in combination.

Hereinafter, preferred examples of the (A) acetal resin used in the present invention are exemplified, but the present invention is not limited thereto.
In addition, the weight average molecular weight of (A) acetal type resin illustrated below is 2,000-30,000. The composition ratio is shown in mol% in ().
1-ethoxyethyl methacrylate / methacrylic acid / glycidyl methacrylate / 2-hydroxyethyl methacrylate copolymer (45/8/35/12),
Tetrahydrofuran-2-yl methacrylate / methacrylic acid / glycidyl methacrylate / 2-hydroxyethyl methacrylate copolymer (40/10/30/20),
1-ethoxyethyl methacrylate / methacrylic acid / glycidyl methacrylate / 2-hydroxyethyl methacrylate / dicyclopentanyl methacrylate copolymer (42/11/25/18/4),
1-ethoxyethyl methacrylate / methacrylic acid / glycidyl methacrylate / 2-hydroxyethyl methacrylate / cyclohexyl methacrylate methacrylate (35/10/30/20/5),
1-ethoxyethyl methacrylate / methacrylic acid / glycidyl methacrylate / poly (ethylene glycol / propylene glycol) -monomethacrylate (Blenmer 50PEP-300, manufactured by NOF Corporation) / dicyclopentanyl methacrylate copolymer (55 / 9/30/2/4),
1-ethoxyethyl methacrylate / methacrylic acid / glycidyl methacrylate / methoxypolyethylene glycol methacrylate (Blenmer PME-400, manufactured by NOF Corporation) copolymer (44 / 4.5 / 50 / 1.5),
1-cyclohexyloxyethyl methacrylate / acrylic acid / glycidyl methacrylate / methoxypolyethylene glycol methacrylate (Blenmer PME-400, manufactured by NOF Corporation) copolymer (45/10/43/2),
1-cyclohexyloxyethyl methacrylate / methacrylic acid / glycidyl methacrylate / methoxypolyethylene glycol methacrylate (Blenmer PME-400, manufactured by NOF Corporation) / dicyclopentanyl methacrylate copolymer (43/15/30/2 / 10), tetrahydro-2H-pyran-2-yl methacrylate / methacrylic acid / glycidyl methacrylate / 2-hydroxyethyl methacrylate copolymer (40/12/28/20),
1-ethoxyethyl methacrylate / methacrylic acid / methacrylic acid (3-ethyloxetane-3-yl) methyl / 2-hydroxyethyl methacrylate copolymer (40/10/30/20),
Tetrahydrofuran-2-yl methacrylate / methacrylic acid / methacrylic acid (3-ethyloxetane-3-yl) methyl / 2-hydroxyethyl methacrylate copolymer (40/10/30/20),

1-ethoxyethyl methacrylate / methacrylic acid / methacrylic acid (3-ethyloxetane-3-yl) methyl / methoxypolyethyleneglycol methacrylate (Blenmer PME-400, manufactured by NOF Corporation) copolymer (40/10/46) / 4),
1-ethoxyethyl methacrylate / methacrylic acid / methacrylic acid (3-ethyloxetane-3-yl) methyl / methoxypolyethylene glycol methacrylate (Blenmer PME-400, manufactured by NOF Corporation) / 2-hydroxyethyl methacrylate Coalescence (45/10/30/1/14),
1-ethoxyethyl methacrylate / methacrylic acid / methacrylic acid (3-ethyloxetane-3-yl) methyl / 2-hydroxyethyl methacrylate / dicyclopentanyl methacrylate copolymer (40/10/25/20/5 ),
1-ethoxyethyl methacrylate / methacrylic acid / methacrylic acid (3-ethyloxetane-3-yl) methyl / 2-hydroxyethyl methacrylate / methyl methacrylate copolymer (38/7/35/15/5),
1-ethoxyethyl methacrylate / methacrylic acid / methacrylic acid (3-ethyloxetane-3-yl) methyl / methoxypolyethyleneglycol methacrylate (Blenmer PME-200, manufactured by NOF Corporation) copolymer (50/8/37) / 5),
1-ethoxyethyl methacrylate / methacrylic acid / methacrylic acid (3-ethyloxetane-3-yl) methyl / methacrylic acid 2,3-dihydroxypropyl copolymer (40/7/30/23),
1-cyclohexyloxyethyl methacrylate / methacrylic acid / methacrylic acid (3-ethyloxetane-3-yl) methyl / methoxypolyethylene glycol methacrylate (Blenmer PME-400, manufactured by NOF Corporation) copolymer (41/14 / 41/4),
1-cyclohexyloxyethyl methacrylate / methacrylic acid / methacrylic acid (3-ethyloxetane-3-yl) methyl / 2-hydroxyethyl methacrylate copolymer (40/10/25/25),
Tetrahydro-2H-pyran-2-yl methacrylate / methacrylic acid / methacrylic acid (3-ethyloxetane-3-yl) methyl / methacrylic acid 2,3-dihydroxypropyl copolymer (40/5/30/25),
1-cyclohexyloxyethyl methacrylate / acrylic acid / acrylic acid (3-ethyloxetane-3-yl) methyl / methoxypolyethyleneglycol methacrylate (Blenmer PME-200, manufactured by NOF Corporation) copolymer (40/12 / 44/4),
1-ethoxyethyl methacrylate / methacrylic acid / acrylic acid (3-ethyloxetane-3-yl) methyl / 2-hydroxyethyl methacrylate copolymer (40/10/32/18),
1-ethoxyethyl methacrylate / methacrylic acid / 3,4-epoxycyclohexylmethyl methacrylate / 2-hydroxyethyl methacrylate copolymer (40/5/35/20),
1-ethoxyethyl methacrylate / acrylic acid / 3,4-epoxycyclohexylmethyl methacrylate / methoxypolyethylene glycol methacrylate (Blenmer PME-200, manufactured by NOF Corporation) / methyl methacrylate copolymer (40/15/35 / 5/5),
1-ethoxyethyl methacrylate / 4-hydroxybenzoic acid (3-methacryloyloxy-2-hydroxypropyl) ester / glycidyl methacrylate / 2-hydroxyethyl methacrylate copolymer (30/12/38/20),
1-ethoxyethyl methacrylate / 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester / glycidyl methacrylate / 2-hydroxyethyl methacrylate copolymer (40/7/35/18),
(A) Acetal type resin can be used individually by 1 type or in combination of 2 or more types to a chemical amplification type positive photosensitive composition.

The content ratio of the structural units (a1) to (a5) in the (A) acetal resin is expressed in terms of moles when the (A) acetal resin is 1, the structural unit (a1): the structural unit (a2): the structure Unit (a3): Structural unit (a4): Structural unit (a5) = (0.2-0.65): (0.02-0.2): (0.2-0.60): (0. 005-0.3): (0-0.4), (0.25-0.6): (0.02-0.15): (0.25-0.55): (0. 005 to 0.25): (0 to 0.3) is more preferable, (0.25 to 0.55): (0.03 to 0.15): (0.25 to 0.5) : (0.01 to 0.25): (0 to 0.25) is more preferable.
Further, in all the structural units constituting the (A) acetal resin, the content of the structural unit (a4) is 3 to 30% by mass, more preferably 3 to 25% by mass, and particularly preferably 5 to 25% by mass. .

The content of the (A) acetal resin in the chemically amplified positive photosensitive composition of the present invention is preferably 30 to 95% by mass with respect to the total solid content of the chemically amplified positive photosensitive composition. More preferably, it is 25-90 mass%, and it is still more preferable that it is 30-80 mass%. When the content is within this range, the pattern formability upon development is good. The solid content of the chemically amplified positive photosensitive composition represents an amount excluding volatile components such as a solvent.
In the chemically amplified positive photosensitive composition of the present invention, a resin other than the (A) acetal resin may be used in combination as long as the effects of the present invention are not hindered. However, the content of the resin other than the (A) acetal resin is preferably smaller than the content of the (A) acetal resin from the viewpoint of developability.

(B) Photoacid generator The chemically amplified positive photosensitive composition of the present invention comprises (B) a compound that generates an acid upon irradiation with actinic rays and / or radiation (hereinafter referred to as “(B) a photoacid generator”. Contain).
The photoacid generator (B) used in the present invention is preferably a compound that reacts with an actinic ray having a wavelength of 300 nm or more, preferably 300 to 450 nm, and generates an acid, but is limited to its chemical structure. is not. Further, a photoacid generator that is not directly sensitive to an actinic ray having a wavelength of 300 nm or more can also be used as a sensitizer if it is a compound that reacts with an actinic ray having a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer. It can be preferably used in combination.
The photoacid generator used in the present invention is preferably a photoacid generator that generates an acid having a pKa of 4 or less, and more preferably a photoacid generator that generates an acid having a pKa of 3 or less.
Examples of the photoacid generator include trichloromethyl-s-triazines, sulfonium salts and iodonium salts, quaternary ammonium salts, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. Among these, it is preferable to use an oxime sulfonate compound from the viewpoint of high sensitivity. These photoacid generators can be used singly or in combination of two or more.

Specific examples of these include the following.
As trichloromethyl-s-triazines, 2- (3-chlorophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -bis (4,6-trichloromethyl)- s-triazine, 2- (4-methylthiophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methoxy-β-styryl) -bis (4,6-trichloromethyl) -s -Triazine, 2-piperonyl-bis (4,6-trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -bis (4,6-trichloromethyl) -s-triazine, 2- [2- (5-Methylfuran-2-yl) ethenyl] -bis (4,6-trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methyl) Butylphenyl) ethenyl] - bis (4,6-trichloromethyl) -s-triazine, or 2- (4-methoxynaphthyl) - bis (4,6-trichloromethyl) -s-triazine.

  Examples of diaryliodonium salts include diphenyliodonium trifluoroacetate, diphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoroacetate, phenyl-4- (2′-hydroxy-1) '-Tetradecaoxy) phenyliodonium trifluoromethanesulfonate, 4- (2'-hydroxy-1'-tetradecaoxy) phenyliodonium hexafluoroantimonate, or phenyl-4- (2'-hydroxy-1'-) Tetradecaoxy) phenyliodonium p-toluenesulfonate and the like.

  Examples of triarylsulfonium salts include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyldiphenylsulfonium trifluoroacetate, 4-phenylthiophenyldiphenylsulfonium trifluoro. Lomethanesulfonate or 4-phenylthiophenyldiphenylsulfonium trifluoroacetate.

  As quaternary ammonium salts, tetramethylammonium butyltris (2,6-difluorophenyl) borate, tetramethylammonium hexyltris (p-chlorophenyl) borate, tetramethylammonium hexyltris (3-trifluoromethylphenyl) borate, benzyl Dimethylphenylammonium butyltris (2,6-difluorophenyl) borate, benzyldimethylphenylammonium hexyltris (p-chlorophenyl) borate, benzyldimethylphenylammonium hexyltris (3-trifluoromethylphenyl) borate and the like.

  Examples of the diazomethane derivative include bis (cyclohexylsulfonyl) diazomethane, bis (t-butylsulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, and the like;

Examples of imide sulfonate derivatives include trifluoromethylsulfonyloxybicyclo [2.2.1] -hept-5-ene-dicarboximide, succinimide trifluoromethyl sulfonate, phthalimide trifluoromethyl sulfonate, N-hydroxynaphthalimide methane sulfonate, N-hydroxy. -5-norbornene-2,3-dicarboximidopropane sulfonate and the like.

  The chemically amplified positive photosensitive composition of the present invention preferably contains (B) an oxime sulfonate compound having at least one oxime sulfonate group represented by the following structure (1) as a photoacid generator.

The oxime sulfonate compound having at least one oxime sulfonate group represented by the structure (1) is preferably a compound represented by the following general formula (2).
^{R 1A -C (R 2A) =} N-O-SO 2 -R 3A (2)

In general formula (2), R ^1A is an alkyl group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, a phenyl group, a biphenyl group, a naphthyl group, a 2-furyl group, or 2-thienyl. Group, an alkoxy group having 1 to 4 carbon atoms or a cyano group, and when R ^1A is a phenyl group, a biphenyl group, a naphthyl group or an anthranyl group, these groups are a halogen atom, a hydroxyl group, a carbon atom It may be substituted with a substituent selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms and a nitro group. R ^2A is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, or W It represents a phenyl group which may be substituted, a naphthyl group which may be substituted with W, an anthranyl group which may be substituted with W, a dialkylamino group, a morpholino group, or a cyano group. R ^2A and R ^1A may be bonded to each other to form a 5-membered ring or a 6-membered ring, and the 5-membered ring or 6-membered ring may have one or two arbitrary substituents. It may be bonded to a benzene ring. R ^3A is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, or W It represents a phenyl group which may be substituted, a naphthyl group which may be substituted with W, or an anthranyl group which may be substituted with W. W is a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms. Represents a halogenated alkoxy group.

The alkyl group having 1 to 6 carbon atoms represented by R ^1A may be a linear or branched alkyl group, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec- A butyl group, a tert-butyl group, an n-pentyl group, an isoamyl group, an n-hexyl group, or a 2-ethylbutyl group is exemplified.

Examples of the halogenated alkyl group having 1 to 4 carbon atoms represented by R ^1A include a chloromethyl group, a trichloromethyl group, a trifluoromethyl group, and a 2-bromopropyl group.

Examples of the alkoxy group having 1 to 4 carbon atoms represented by R ^1A include a methoxy group or an ethoxy group.

When R ^1A represents a phenyl group, a biphenyl group, a naphthyl group or an anthranyl group, these groups are a halogen atom (for example, a chlorine atom, a bromine atom, an iodine atom, etc.), a hydroxyl group, and a carbon atom having 1 to 4 carbon atoms. Alkyl groups (for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group), alkoxy groups having 1 to 4 carbon atoms (for example, methoxy group, ethoxy group) , N-propoxy group, i-propoxy group, n-butoxy group) and a substituent selected from the group consisting of nitro groups.

Specific examples of the alkyl group having 1 to 10 carbon atoms represented by R ^2A include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, and s-butyl. Group, t-butyl group, n-amyl group, i-amyl group, s-amyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group and the like. .

Specific examples of the alkoxy group having 1 to 10 carbon atoms represented by R ^2A include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, n-amyloxy group and n-octyl. An oxy group, n-decyloxy group, etc. are mentioned.

Specific examples of the halogenated alkyl group having 1 to 5 carbon atoms represented by R ^2A include trifluoromethyl group, pentafluoroethyl group, perfluoro-n-propyl group, perfluoro-n-butyl group, perfluoro group. Examples include a fluoro-n-amyl group.

Specific examples of the halogenated alkoxy group having 1 to 5 carbon atoms represented by R ^2A include a trifluoromethoxy group, a pentafluoroethoxy group, a perfluoro-n-propoxy group, a perfluoro-n-butoxy group, a perfluoro group. Examples include a fluoro-n-amyloxy group.

Specific examples of the phenyl group optionally substituted by W represented by R ^2A include o-tolyl group, m-tolyl group, p-tolyl group, o-ethylphenyl group, m-ethylphenyl group, p -Ethylphenyl group, p- (n-propyl) phenyl group, p- (i-propyl) phenyl group, p- (n-butyl) phenyl group, p- (i-butyl) phenyl group, p- (s- Butyl) phenyl group, p- (t-butyl) phenyl group, p- (n-amyl) phenyl group, p- (i-amyl) phenyl group, p- (t-amyl) phenyl group, o-methoxyphenyl group , M-
Methoxyphenyl group, p-methoxyphenyl group, o-ethoxyphenyl group, m-ethoxyphenyl group, p-ethoxyphenyl group, p- (n-propoxy) phenyl group, p- (i-propoxy) phenyl group, p- (N-butoxy) phenyl group, p- (i-butoxy) phenyl group, p- (s-butoxy) phenyl group, p- (t-butoxy) phenyl group, p- (n-amyloxy) phenyl group, p- (I-amyloxy) phenyl group, p- (t-amyloxy) phenyl group, p-chlorophenyl group, p-bromophenyl group, p-fluorophenyl group, 2,4-dichlorophenyl group, 2,4-dibromo Phenyl group, 2,4-difluorophenyl group, 2,4,6-dichlorophenyl group, 2,4,6-tribromophenyl group, 2,4,6-trifluorophenyl Nyl group, pentachlorophenyl group, pentabromophenyl group, pentafluorophenyl group, p-biphenylyl group and the like can be mentioned.

Specific examples of the naphthyl group optionally substituted by W represented by R ^2A include 2-methyl-1-naphthyl group, 3-methyl-1-naphthyl group, 4-methyl-1-naphthyl group, 5 -Methyl-1-naphthyl group, 6-methyl-1-naphthyl group, 7-methyl-1-naphthyl group, 8-methyl-1-naphthyl group, 1-methyl-2-naphthyl group, 3-methyl-2- Naphthyl group, 4-methyl-2-naphthyl group, 5-methyl-2-naphthyl group, 6-methyl-2-naphthyl group, 7-methyl-2-naphthyl group, 8-methyl-2-naphthyl group, etc. It is done.

Specific examples of the anthranyl group optionally substituted with W represented by R ^2A include a 2-methyl-1-anthranyl group, a 3-methyl-1-anthranyl group, a 4-methyl-1-anthranyl group, 5 -Methyl-1-anthranyl group, 6-methyl-1-anthranyl group, 7-methyl-1-anthranyl group, 8-methyl-1-anthranyl group, 9-methyl-1-anthranyl group, 10-methyl-1- Anthranyl group, 1-methyl-2-anthranyl group, 3-methyl-2-anthranyl group, 4-methyl-2-anthranyl group, 5-methyl-2-anthranyl group, 6-methyl-2-anthranyl group, 7- Examples thereof include a methyl-2-anthranyl group, an 8-methyl-2-anthranyl group, a 9-methyl-2-anthranyl group, and a 10-methyl-2-anthranyl group.

^Examples of the dialkylamino group represented by R ^2A include a dimethylamino group, a diethylamino group, a dipropylamino group, a dibutylamino group, and a diphenylamino group.

Specific examples of the alkyl group having 1 to 10 carbon atoms represented by R ^3A include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, and s-butyl. Group, t-butyl group, n-amyl group, i-amyl group, s-amyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group and the like. .

Specific examples of the alkoxy group having 1 to 10 carbon atoms represented by R ^3A include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, n-amyloxy group and n-octyl. An oxy group, n-decyloxy group, etc. are mentioned.

Specific examples of the halogenated alkyl group having 1 to 5 carbon atoms represented by R ^3A include trifluoromethyl group, pentafluoroethyl group, perfluoro-n-propyl group, perfluoro-n-butyl group, perfluoro group. Examples include a fluoro-n-amyl group.

Specific examples of the halogenated alkoxy group having 1 to 5 carbon atoms represented by R ^3A include a trifluoromethoxy group, a pentafluoroethoxy group, a perfluoro-n-propoxy group, a perfluoro-n-butoxy group, a perfluoro group. Examples include a fluoro-n-amyloxy group.

Specific examples of the phenyl group optionally substituted by W represented by R ^3A include o-tolyl group, m-tolyl group, p-tolyl group, o-ethylphenyl group, m-ethylphenyl group, p -Ethylphenyl group, p- (n-propyl) phenyl group, p- (i-propyl) phenyl group, p- (n-butyl) phenyl group, p- (i-butyl) phenyl group, p- (s- Butyl) phenyl group, p- (t-butyl) phenyl group, p- (n-amyl) phenyl group, p- (i-amyl) phenyl group, p- (t-amyl) phenyl group, o-methoxyphenyl group , M-
Methoxyphenyl group, p-methoxyphenyl group, o-ethoxyphenyl group, m-ethoxyphenyl group, p-ethoxyphenyl group, p- (n-propoxy) phenyl group, p- (i-propoxy) phenyl group, p- (N-butoxy) phenyl group, p- (i-butoxy) phenyl group, p- (s-butoxy) phenyl group, p- (t-butoxy) phenyl group, p- (n-amyloxy) phenyl group, p- (I-amyloxy) phenyl group, p- (t-amyloxy) phenyl group, p-chlorophenyl group, p-bromophenyl group, p-fluorophenyl group, 2,4-dichlorophenyl group, 2,4-dibromo Phenyl group, 2,4-difluorophenyl group, 2,4,6-dichlorophenyl group, 2,4,6-tribromophenyl group, 2,4,6-trifluorophenyl Nyl group, pentachlorophenyl group, pentabromophenyl group, pentafluorophenyl group, p-biphenylyl group and the like can be mentioned.

Specific examples of the naphthyl group optionally substituted by W represented by R ^3A include 2-methyl-1-naphthyl group, 3-methyl-1-naphthyl group, 4-methyl-1-naphthyl group, 5 -Methyl-1-naphthyl group, 6-methyl-1-naphthyl group, 7-methyl-1-naphthyl group, 8-methyl-1-naphthyl group, 1-methyl-2-naphthyl group, 3-methyl-2- Naphthyl group, 4-methyl-2-naphthyl group, 5-methyl-2-naphthyl group, 6-methyl-2-naphthyl group, 7-methyl-2-naphthyl group, 8-methyl-2-naphthyl group, etc. It is done.

Specific examples of the anthranyl group optionally substituted with W represented by R ^3A include a 2-methyl-1-anthranyl group, a 3-methyl-1-anthranyl group, a 4-methyl-1-anthranyl group, 5 -Methyl-1-anthranyl group, 6-methyl-1-anthranyl group, 7-methyl-1-anthranyl group, 8-methyl-1-anthranyl group, 9-methyl-1-anthranyl group, 10-methyl-1- Anthranyl group, 1-methyl-2-anthranyl group, 3-methyl-2-anthranyl group, 4-methyl-2-anthranyl group, 5-methyl-2-anthranyl group, 6-methyl-2-anthranyl group, 7- Examples thereof include a methyl-2-anthranyl group, an 8-methyl-2-anthranyl group, a 9-methyl-2-anthranyl group, and a 10-methyl-2-anthranyl group.

Specific examples of an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, and a halogenated alkoxy having 1 to 5 carbon atoms represented by W Examples include an alkyl group having 1 to 10 carbon atoms represented by R ^2A or R ^3A , an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, and 1 carbon atom. The thing similar to what was mentioned as a specific example of the halogenated alkoxy group of -5 is mentioned.

R ^2A and R ^1A may be bonded to each other to form a 5-membered ring or a 6-membered ring.
When R ^2A and R ^1A are bonded to each other to form a 5-membered ring or a 6-membered ring, examples of the 5-membered ring or 6-membered ring include a carbocyclic group and a heterocyclic ring group. It may be a cyclopentane, cyclohexane, cycloheptane, pyrrole, furan, thiophene, imidazole, oxazole, thiazole, pyran, pyridine, pyrazine, morpholine, piperidine or piperazine ring. The 5-membered ring or 6-membered ring may be bonded to an optionally substituted benzene ring, and examples thereof include tetrahydronaphthalene, dihydroanthracene, indene, chroman, fluorene, xanthene or thiol. Xanthene ring system. The 5-membered or 6-membered ring may contain a carbonyl group, examples of which include cyclohexadienone, naphthalenone and anthrone ring systems.

One of the suitable aspects of the compound represented by General formula (2) is a compound represented by the following general formula (2-1). The compound represented by the general formula (2-1) is a compound in which R ^2A and R ^1A in the general formula (2) are bonded to form a 5-membered ring.

In General Formula (2-1), R ^3A has the same meaning as R ^3A in General Formula (2), X represents an alkyl group, an alkoxy group, or a halogen atom, and t represents an integer of 0 to 3. And when t is 2 or 3, the plurality of X may be the same or different.

The alkyl group represented by X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms.
The alkoxy group represented by X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms.
As the halogen atom represented by X, a chlorine atom or a fluorine atom is preferable.
t is preferably 0 or 1.

In general formula (2-1), t is 1, X is a methyl group, the substitution position of X is an ortho position, R ^3A is a linear alkyl group having 1 to 10 carbon atoms, 7, A compound which is a 7-dimethyl-2-oxonorbornylmethyl group or a p-toluyl group is particularly preferable.

  Specific examples of the oxime sulfonate compound represented by the general formula (2-1) include the following compound (i), compound (ii), compound (iii), compound (iv), and the like. One kind may be used alone, or two or more kinds may be used in combination. Compounds (i) to (iv) can be obtained as commercial products.

As one of the preferable embodiments of the photoacid stopper represented by the general formula (2), R ^1A is an alkyl group having 1 to 4 carbon atoms, a trifluoromethyl group, a phenyl group, a chlorophenyl group, or a dichlorophenyl group. Represents a methoxyphenyl group, a 4-biphenyl group, a naphthyl group or an anthranyl group;
R ^2A represents a cyano group;
R ^3A is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, or W A phenyl group which may be substituted, a naphthyl group which may be substituted with W, or an anthranyl group which may be substituted with W, W represents a halogen atom, a cyano group, a nitro group, or a carbon atom number of 1 Represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or a halogenated alkoxy group having 1 to 5 carbon atoms.

  The compound represented by the general formula (2) is preferably a compound represented by the following general formula (2-2).

In General Formula (2-2), R ^4A represents a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a nitro group, and l is 0 to 5 Represents an integer. R ^3A is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, or W A phenyl group which may be substituted, a naphthyl group which may be substituted with W, or an anthranyl group which may be substituted with W, W represents a halogen atom, a cyano group, a nitro group, a carbon number of 1 to 1 10 represents an alkyl group, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or a halogenated alkoxy group having 1 to 5 carbon atoms.

R ^3A in the general formula (2-2) is methyl group, ethyl group, n-propyl group, n-butyl group, n-octyl group, trifluoromethyl group, pentafluoroethyl group, perfluoro-n-propyl. Group, perfluoro-n-butyl group, p-tolyl group, 4-chlorophenyl group or pentafluorophenyl group is preferable, and it is methyl group, ethyl group, n-propyl group, n-butyl group or p-tolyl group. Is particularly preferred.
The halogen atom represented by R ^4A is preferably a fluorine atom, a chlorine atom or a bromine atom.
The alkyl group having 1 to 4 carbon atoms represented by R ^4A is preferably a methyl group or an ethyl group.
The alkoxy group having 1 to 4 carbon atoms represented by R ^4A is preferably a methoxy group or an ethoxy group.
As l, 0-2 are preferable and 0-1 are particularly preferable.

Among the photoacid generators represented by the general formula (2), preferred embodiments of the compounds included in the photoacid generator represented by the general formula (2-2) include R in the general formula (2). ^In a mode in which ^1A represents a phenyl group or a 4-methoxyphenyl group, R ^2A represents a cyano group, and R ^3A represents a methyl group, an ethyl group, an n-propyl group, an n-butyl group, or a 4-tolyl group. is there.

  Hereinafter, among the photoacid generators represented by the general formula (2), particularly preferred examples of the compounds included in the photoacid generator represented by the general formula (2-2) are shown. It is not limited to.

α- (methylsulfonyloxyimino) benzyl cyanide (R ^1A = phenyl group, R ^2A = -CN group, R ^3A = methyl group)
α- (Ethylsulfonyloxyimino) benzyl cyanide (R ^1A = phenyl group, R ^2A = -CN group, R ^3A = ethyl group)
α- (n-propylsulfonyloxyimino) benzyl cyanide (R ^1A = phenyl group, R ^2A = -CN group, R ^3A = n-propyl group)
α- (n-butylsulfonyloxyimino) benzyl cyanide (R ^1A = phenyl group, R ^2A = -CN group, R ^3A = n-butyl group)
α- (4-Toluenesulfonyloxyimino) benzyl cyanide (R ^1A = phenyl group, R ^2A = -CN group, R ^3A = 4-tolyl group)
α-[(Methylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile (R ^1A = 4-methoxyphenyl group, R ^2A = -CN group, R ^3A = methyl group)
α-[(Ethylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile (R ^1A = 4-methoxyphenyl group, R ^2A = -CN group, R ^3A = ethyl group)
α-[(n-propylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile (R ^1A = 4-methoxyphenyl group, R ^2A = -CN group, R ^3A = n-propyl group)
α-[(n-butylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile (R ^1A = 4-methoxyphenyl group, R ^2A = -CN group, R ^3A = n-butyl group)
α-[(4-Toluenesulfonyloxyimino) -4-methoxyphenyl] acetonitrile (R ^1A = 4-methoxyphenyl group, R ^2A = -CN group, R ^3A = 4-tolyl group)

  In the chemically amplified positive photosensitive composition of the present invention, (B) the photoacid generator is used in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass of the compound (A) whose alkali solubility increases with acid. It is more preferable to use 0.5 to 10 parts by mass.

(C) Crosslinking agent In this invention, the crosslinking agent which is represented by Formula (I) and whose number average molecular weight is 600-2000 is used as a crosslinking agent.
Formula (I)
(In formula (I), A is composed of —O— and a divalent organic group, and includes at least a partial structure represented by the following formula (I-2).)
Formula (I-2)
(X represents a divalent organic group.)
R ¹ is preferably a hydrogen atom or a methyl group.
A is preferably a formula (I-2), -O - , - CH 2 -, - CH (CH 3) -, - a combination of one or more of the X- and -Ar-. Here, -X- and -Ar- are synonymous with -X- and -Ar- in formula (II) described later, and their preferred ranges are also synonymous.

The crosslinking agent (C) used in the present invention is also preferably a crosslinking agent represented by the following formula.
(In the above formula, Ra and Rb each represent a hydrogen atom, a methyl group, an ethyl group, an isopropyl group or a butyl group, and Rc, Rd, Re and Rf are each a hydrogen atom or an alkyl having 1 to 9 carbon atoms. Represents a group, c is an integer of 1 to 7, and n is an integer of 1 to 20. When n is 2 or more, each Ra and Rb may be the same or different.
Such a crosslinking agent can be synthesized in consideration of the description in JP-A-5-65331. The preferred range is also synonymous with that described in JP-A-5-65331.

The crosslinking agent (C) used in the present invention is also preferably a crosslinking agent represented by the following formula.

The crosslinking agent used in the present invention is more preferably a crosslinking agent represented by formula (II) or formula (III).
Crosslinker represented by formula (II) (II)
(In the formula (II), Ar represents an aromatic hydrocarbon group, X represents a divalent organic group, and n is an integer of 1 to 20.)
Ar may be the same or different.
Ar is (i) an aromatic hydrocarbon group having a structure having only one benzene ring, (ii) an aromatic hydrocarbon having a structure in which the benzene rings are bonded via a single bond, and (iii) the benzene ring is fatty. An aromatic hydrocarbon having a structure bonded via an aromatic carbon atom, and (iv) an aromatic hydrocarbon having a structure having a benzene ring bonded via an aliphatic cyclic hydrocarbon group, and (v) a plurality of benzene rings. An aromatic hydrocarbon having a condensed polycyclic structure and (vi) a hydrocarbon group having a structure in which a benzene ring is bonded via an aralkyl group can be mentioned.

Specifically, as Ar, a phenylene group having a binding site at o-, m- or p-, 4,4'-biphenylene group, 2,2'6,6'-tetramethyl-4,4'- Biphenyl group, methylenediphenylene group, 2,2-propane-diphenyl group,

(In the structural formula iv-1 and the structural formula iv-3, the bonding position of the aliphatic cyclic hydrocarbon group is any secondary carbon atom of ethylene or propylene forming the ring.)

1,6-naphthalene group, naphthalene group such as 2,7-naphthalene group, 1,4-naphthalene group, 1,5-naphthalene group, 2,3-naphthalene group,
Is exemplified.

Among these, a methylenediphenylene group, a 2,2-propane-diphenyl group, or any of the followings is preferable.
More preferred is a methylenediphenylene group or a 2,2-propane-diphenyl group.

  X represents a divalent organic group, ethyleneoxyethyl group, di (ethyleneoxy) ethyl group, tri (ethyleneoxy) ethyl group, tetra (ethyleneoxy) ethyl group, propyleneoxypropyl group, di (propyleneoxy) Propyl group, tri (propyleneoxy) propyl group, tetra (propyleneoxy) propyl group, butyleneoxybutyl group, di (butyleneoxy) butyl group, tri (butyleneoxy) butyl group, tetra (butyleneoxy) butyl group, carbon atom It is preferably selected from an alkylene group having 2 to 15 carbon atoms and an aliphatic hydrocarbon group having 6 to 17 carbon atoms having a cycloalkane skeleton. More preferably, ethyleneoxyethyl group, di (ethyleneoxy) ethyl group, tri (ethyleneoxy) ethyl group, propyleneoxypropyl group, di (propyleneoxy) propyl group, tri (propyleneoxy) propyl group, 2 carbon atoms It is selected from an aliphatic hydrocarbon group having 6 to 17 carbon atoms having a -15 alkylene group or a cycloalkane skeleton. More preferably, ethyleneoxyethyl group, di (ethyleneoxy) ethyl group, tri (ethyleneoxy) ethyl group, propyleneoxypropyl group, di (propyleneoxy) propyl group, tri (propyleneoxy) propyl group and 2 carbon atoms. Selected from ˜15 alkylene groups.

n is an integer of 1 to 20, preferably 2 to 10, and more preferably 3 to 8.
More specifically, the compound represented by formula (II) is more preferably a compound represented by any one of the following general formulas 1 to 3, and particularly preferably represented by general formula 1.

(Wherein R ₁ and R ₂ each represent a hydrogen atom or a methyl group, and R _{3 to} R ₆ each represent a hydrogen atom, a methyl group, a chlorine atom, or a bromine atom. X represents an ethyleneoxyethyl group, di (ethylene An oxy) ethyl group, a tri (ethyleneoxy) ethyl group, a propyleneoxypropyl group, a di (propyleneoxy) propyl group, a tri (propyleneoxy) propyl group, or an alkylene group having 2 to 15 carbon atoms, and n. Is a natural number and the average is 1.2-5.)

(In the formula, R ₁ and R ₂ each represent a hydrogen atom or a methyl group, R _{3 to} R ₆ each represent a hydrogen atom, a methyl group, a chlorine atom, or a bromine atom. X represents the number of carbon atoms having a cycloalkane skeleton. 6 to 17 aliphatic hydrocarbon groups, and n is a natural number and the average value is 1.2 to 5.)

(Wherein R _{3 to} R ₆ each represent a hydrogen atom, a methyl group, a chlorine atom, or a bromine atom. X independently represents an aliphatic hydrocarbon group having 6 to 17 carbon atoms having a cycloalkane skeleton. In addition, n is a natural number and the average value is 1.2 to 5.)

Examples of the compound represented by the formula (II) used in the present invention are shown below. Needless to say, the present invention is not limited to these examples.

  JP, 2004-156024, A can be referred to for details, such as a manufacturing method of these compounds.

Crosslinker represented by formula (III)
(In formula (III), R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and X and Y each independently represent a divalent organic group. N is an integer of 0 to 20. )

R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.
X and Y are ethyleneoxyethyl group, di (ethyleneoxy) ethyl group, tri (ethyleneoxy) ethyl group, tetra (ethyleneoxy) ethyl group, propyleneoxypropyl group, di (propyleneoxy) propyl group, tri (Propyleneoxy) propyl group, tetra (propyleneoxy) propyl group, butyleneoxybutyl group, di (butyleneoxy) butyl group, tri (butyleneoxy) butyl group, tetra (butyleneoxy) butyl group, 2-15 carbon atoms And an aliphatic hydrocarbon group having 6 to 17 carbon atoms having a cycloalkane skeleton. More preferably, di (ethyleneoxy) ethyl group, tri (ethyleneoxy) ethyl group, tetra (ethyleneoxy) ethyl group, propyleneoxypropyl group, di (propyleneoxy) propyl group, tri (propyleneoxy) propyl group, tetra They are (propyleneoxy) propyl group, butyleneoxybutyl group, di (butyleneoxy) butyl group, tri (butyleneoxy) butyl group, and tetra (butyleneoxy) butyl group.
n is an integer of 0 to 20, preferably 1 to 10, and more preferably 2 to 6.
Details of the method for producing the compound represented by the formula (III) can be referred to the description in JP-A No. 2006-111810.

The epoxy resin represented by the formula (I) is preferably composed of only hydrogen atoms, oxygen atoms, and carbon atoms.
The epoxy resin represented by the formula (I) used in the present invention has a lower epoxy equivalent, the lower the viscosity of the epoxy resin, but it is 200 g / eq or more because the cured product has good flexibility. In addition, it is preferably 3000 g / eq or less because fluidity and workability are good. More preferably, it is 300-2000 g / eq.

  Further, the number average molecular weight of the epoxy resin represented by the formula (I) used in the present invention is preferably 400 or more because the cured product has good flexibility. From the viewpoint of good properties, it is preferably 4000 or less, particularly preferably 600 to 2000.

  In addition, the epoxy resin represented by the formula (I) used in the present invention has a viscosity at 25 ° C. of 2000 mPa · s or less in many aspects such as fluidity, workability, and freedom of composition blending. preferable. More preferably, the viscosity under the same conditions is 500 mPa · s or less.

  Moreover, the epoxy resin represented by the formula (I) used in the present invention is preferable because the total chlorine content (after sodium metal treatment in butanol solution and silver nitrate titration method) is 50 ppm or less, and the moisture resistance reliability is excellent. More preferably, it is 10 ppm or less.

  The epoxy resin represented by the formula (I) used in the present invention is used as a cross-linking agent, and may be included in the composition of the present invention only in one kind or in two or more kinds. good. The content of the epoxy resin represented by the formula (I) is preferably 10 to 80 parts by weight, preferably 30 to 70 parts by weight with respect to 100 parts by weight of the compound (A) whose alkali solubility is increased by the acid. Part.

<Other ingredients>
In addition to the above components in the chemical amplification type positive photosensitive composition of the present invention, a basic compound, a surfactant, an ultraviolet absorber, a sensitizer, a plasticizer, a thickener, an organic solvent, if necessary An adhesion promoter, an organic or inorganic precipitation inhibitor, and the like can be added.

<Surfactant>
As the surfactant, any of anionic, cationic, nonionic or amphoteric can be used, but a preferred surfactant is a nonionic surfactant. Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone-based and fluorine-based surfactants. it can. The following trade names are KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), F Top (manufactured by JEMCO), Mega Fuck (manufactured by Dainippon Ink and Chemicals), Florard (manufactured by Sumitomo 3M), Asahi Guard, Each series such as Surflon (manufactured by Asahi Glass) PolyFox (manufactured by OMNOVA) can be listed.

Surfactant can be used individually or in mixture of 2 or more types.
The compounding ratio of the surfactant is usually 10 parts by mass or less per 100 parts by mass of the component (A), preferably 0.01 to 10 parts by mass, and more preferably 0.01 to 1 part by mass.

<Solvent>
The positive photosensitive composition of the present invention is used as a solution by dissolving the above components in a solvent. As the solvent used in the positive photosensitive composition of the present invention, for example,
(A) Ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether;
(A) Ethylene glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether;
(C) Ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate;
(D) Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether;
(E) propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether;
(F) Propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate;
(G) Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether;
(H) Diethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monobutyl ether acetate;
(G) Dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether;
(Co) dipropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol ethyl methyl ether;
(Sa) Dipropylene glycol monoalkyl ether acetates such as dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monopropyl ether acetate, dipropylene glycol monobutyl ether acetate;
(L) Lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate, n-butyl lactate, isobutyl lactate, n-amyl lactate, isoamyl lactate;
(S) n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, n-hexyl acetate, 2-ethylhexyl acetate, ethyl propionate, n-propyl propionate, isopropyl propionate, n-butyl propionate, propionate Aliphatic carboxylic acid esters such as isobutyl acid, methyl butyrate, ethyl butyrate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, isobutyl butyrate;
(C) ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3- Ethoxypropion methyl, 3-ethoxypropion ethyl, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, 3-methyl-3-methoxybutyl butyrate, aceto Other esters such as methyl acetate, ethyl acetoacetate, methyl pyruvate, ethyl pyruvate;
(So) ketones such as methyl ethyl ketone, methyl propyl ketone, methyl-n-butyl ketone, methyl isobutyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone;
(Ta) Amides such as N-methylformamide, N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone;
(H) Examples include lactones such as γ-butyrolactone.
In addition, benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonal as necessary for these solvents. , Benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate, propylene carbonate and the like can also be added.

A solvent can be used individually or in mixture of 2 or more types.
The mixing ratio of the solvent is usually 50 to 3,000 parts by mass, preferably 100 to 2,000 parts by mass, and more preferably 100 to 500 parts by mass per 100 parts by mass of the component (A).

<Method for forming cured film>
Next, a method for forming a cured film using the chemically amplified positive photosensitive composition of the present invention will be described.
A chemically amplified positive photosensitive composition according to the present invention is applied onto a substrate and heated to form a coating film on the substrate.

By irradiating the obtained coating film with an actinic ray having a wavelength of 300 nm or more, the component (C) is decomposed to generate an acid. Due to the catalytic action of the generated acid, an acid dissociable group contained in the component (A), for example, an acid dissociable group in the structural unit represented by the general formula (1) contained in the (A) acetal resin However, it dissociates by a hydrolysis reaction, and a carboxyl group is generated. By developing this using an alkali developer, an exposed portion containing a resin having a carboxyl group that is easily dissolved in the alkali developer is removed, and a positive image is formed.
The reaction formula of this hydrolysis reaction is shown below.

  In order to accelerate the hydrolysis reaction, post exposure bake (hereinafter referred to as PEB) can be performed as necessary. However, when the heating temperature becomes high, the generated carboxyl group causes a crosslinking reaction with the epoxy group in the component (B), so that development cannot be performed.

  In addition, by performing PEB at a relatively low temperature, decomposition of the acid dissociable group may be promoted without causing a crosslinking reaction.

  The PEB temperature is preferably 130 ° C. or lower, more preferably 110 ° C. or lower, and particularly preferably 80 ° C. or lower.

Next, by heating the obtained positive image, the acid dissociable group in the general formula (1) is thermally decomposed to generate a carboxyl group, and then cured by crosslinking with the epoxy group in the component (B). A film can be formed. This heating is preferably performed at a high temperature of 150 ° C. or more, more preferably 180 to 250 ° C., particularly preferably 200 to 250 ° C.
The heating time can be appropriately set depending on the heating temperature or the like, but is generally 10 to 90 minutes.

  If a step of irradiating the entire surface with actinic rays is added before the heating step, the crosslinking reaction can be promoted by an acid generated by the irradiation of actinic rays.

  Next, a method for forming a cured film using the chemically amplified positive photosensitive composition of the present invention will be specifically described.

  Preparation method of composition solution: (A) component, (B) component, (C) component and other compounding agents are mixed at a predetermined ratio and in an arbitrary method, and stirred and dissolved to prepare a composition solution. For example, each component can be dissolved in a solvent in advance to obtain a solution, and then mixed at a predetermined ratio to prepare a composition solution. The composition solution prepared as described above can be used after being filtered using a filter having a pore size of 0.2 μm or the like.

<Method for creating coating film>
A desired coating film can be formed by applying the composition solution to a predetermined substrate and removing the solvent by heating (hereinafter referred to as pre-baking). Examples of the substrate include a polarizing plate, a glass plate provided with a black matrix layer and a color filter layer as required, and a transparent conductive circuit layer in manufacturing a liquid crystal display element. The coating method on the substrate is not particularly limited, and for example, a spray method, a roll coating method, a spin coating method, or the like can be used.

  The heating conditions during pre-baking are such that the acid dissociable group in the repeating unit represented by the formula (1) in the (A) component in the unexposed area is dissociated and the (A) component is soluble in the alkali developer. However, it is preferably about 80 to 130 [deg.] C. for about 30 to 120 seconds, although it varies depending on the type and mixing ratio of each component.

<Pattern formation method>
After irradiating the substrate on which the coating film is provided with actinic rays through a mask having a predetermined pattern, heat treatment (PEB) is performed as necessary, and then the exposed portion is removed using a developer to form an image pattern. Form.

  For the emission of actinic rays, low-pressure mercury lamps, high-pressure mercury lamps, ultrahigh-pressure mercury lamps, chemical lamps, excimer laser generators, and the like can be used. Is preferred. Moreover, irradiation light can also be adjusted through spectral filters, such as a long wavelength cut filter, a short wavelength cut filter, and a band pass filter, as needed.

  Examples of the developer include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metals such as sodium bicarbonate and potassium bicarbonate Bicarbonates; ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline hydroxide; aqueous solutions such as sodium silicate and sodium metasilicate can be used. 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 alkaline aqueous solution can also be used as a developer.

The pH of the developer is preferably 10.0 to 14.0.
The development time is usually 30 to 180 seconds, and the development method may be any of a liquid piling method, a dip method and the like. After the development, washing with running water is performed for 30 to 90 seconds, and a desired pattern can be formed.

<Crosslinking process>
For a pattern having an unexposed portion obtained by development, a heating device such as a hot plate or an oven is used to set the oven at a predetermined temperature, for example, 180 to 250 ° C. for a predetermined time, for example, 5 to 30 minutes on the hot plate. Then, by performing heat treatment for 30 to 90 minutes, the acid dissociable group in component (A) is eliminated, a carboxyl group is generated, and the epoxy group in component (B) is cross-linked to have heat resistance and hardness. It is possible to form a protective film and an interlayer insulating film excellent in the above. In addition, when heat treatment is performed, the transparency can be improved by performing the heat treatment in a nitrogen atmosphere.

The positive photosensitive composition of the present invention is preferably used for forming a semiconductor rewiring. Hereinafter, the electronic component and the rewiring layer in the present invention will be described. The electronic component according to the present invention has a pattern formed using a positive photosensitive resin composition. Here, the electronic component includes a semiconductor device, a multilayer wiring board, various electronic devices, and the like. Further, the pattern can be used specifically for forming a surface protective film, an interlayer insulating film of a semiconductor device, an interlayer insulating film of a multilayer wiring board, and the like. The electronic component according to the present invention is not particularly limited except that it has a surface protective film and an interlayer insulating film formed using the composition, and can have various structures.
FIG. 1 is a schematic cross-sectional view showing an example of a wiring structure of a semiconductor device. In FIG. 1, an Al wiring layer (not shown) and a pad portion 15 of an Al wiring layer are formed on a silicon chip. An insulating layer 13 is formed on the upper portion, and a surface protective film layer 14 for the element is further formed. A rewiring layer 16 is formed from the pad portion 15, and the rewiring layer 16 extends to an upper portion of the connection portion 24 with the conductive ball 17. Further, a cover coat layer 19 is formed on the surface protective film layer 14. The rewiring layer 16 is connected to the conductive ball 17 through the barrier metal 20.
In FIG. 1, the positive photosensitive resin composition of the present invention can be used not only as an interlayer insulating layer 11 and a surface protective film layer 14, but also as a material for a cover coat layer 19, a core, a collar, an underfill, and the like. . Since the cured resin using the positive photosensitive resin composition of the present invention is excellent in adhesion with a metal layer such as the Al wiring layer 12 and the rewiring layer 16 or a sealant, and has a high stress relaxation effect, The semiconductor device in which this cured body is used for the cover coat layer 19, the core for rewiring, the collar for balls such as solder, the underfill used in the flip chip, etc. has extremely high reliability. In the range which does not deviate from the gist of the present invention, the description of JP-A-2007-240555 can be referred to.

Hereinafter, the present invention will be described more specifically with reference to examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. In addition, Examples 1-5, 7-9, 12-16, 18 and 19 are reference examples.

Synthesis of polymer (A-1) 34.8 g (0.22 mol) of 1-ethoxyethyl methacrylate, 31.6 g (0.18 mol) of benzyl methacrylate, 8.7 g (0.10 mol) of methacrylic acid and 300 ml of methyl isobutyl ketone was charged into a 500 ml three-necked flask, and a catalytic amount of 2,2′-azobis (methyl 2-methylpropionate) was added as a radical polymerization initiator to the flask. Polymerized for hours. After cooling the reaction solution, it was poured into a large amount of heptane to precipitate a polymer. The crystals were collected by filtration, dissolved in propylene glycol monomethyl ether acetate, and heptane and methyl isobutyl ketone contained in the solution were distilled off under reduced pressure to give polymer A-1 (1-ethoxyethyl methacrylate / benzyl methacrylate). / Methacrylic acid) was obtained as a propylene glycol monomethyl ether acetate solution.
As for the molecular weight and molecular weight distribution of the polymer obtained, GPC measurement using polystyrene as a standard revealed that the weight average molecular weight was about 8,000 and the molecular weight distribution (Mw / Mn) was 1.8.

Synthesis of Polymer (A-2) A polymer (A-2) was obtained by synthesizing in the same manner as the polymer (A-1) except that the monomers used were changed to those in Table 1.
As for the molecular weight and molecular weight distribution of the polymer obtained, GPC measurement using polystyrene as a standard revealed that the weight average molecular weight was about 8,000 and the molecular weight distribution (Mw / Mn) was 1.9.

Synthesis of polymer (A-3) 11.6 g (0.20 mol) of 1-ethoxyethyl methacrylate, 26.4 g (0.15 mol) of glycidyl methacrylate, 13.0 g (0. 10 mol), 4.4 g (0.05 mol) of methacrylic acid and 300 ml of methyl isobutyl ketone were charged into a 500 ml three-necked flask, and a catalytic amount of 2,2′-azobis (2-methyl) was used as a radical polymerization initiator. Methyl propionate) was added, and polymerization was carried out at 80 ° C. for 6 hours under a nitrogen stream. After cooling the reaction solution, it was poured into a large amount of heptane to precipitate a polymer. The crystals were collected by filtration, dissolved in propylene glycol monomethyl ether acetate, and heptane and methyl isobutyl ketone contained in the solution were distilled off under reduced pressure to give polymer A-3 (1-ethoxyethyl methacrylate / glycidyl methacrylate / (2-hydroxyethyl methacrylate / methacrylic acid) was obtained as a propylene glycol monomethyl ether acetate solution.
As for the molecular weight and molecular weight distribution of the polymer obtained, GPC measurement using polystyrene as a standard revealed that the weight average molecular weight was about 8,000 and the molecular weight distribution (Mw / Mn) was 1.7.

Synthesis of Polymers (A-4) to (A-6) A polymer (A-4) to (A-4) was synthesized by synthesizing in the same manner as the polymer (A-3) except that the monomers used were changed to those in Table 1. (A-6) was obtained. The molecular weight and molecular weight distribution of the obtained polymer were as shown in the table.

In the above table, MAEVE represents 1-ethoxyethyl methacrylate (manufactured by Wako Pure Chemical Industries), MABuVE represents (1-butoxyethyl methacrylate), MABuVE and OXE-30 represent 3-ethyl-3-oxetanylmethyl methacrylate (Osaka) GMA represents glycidyl methacrylate (manufactured by Wako Pure Chemical Industries), BzMA represents benzyl methacrylate (manufactured by Wako Pure Chemical Industries), HEMA represents hydroxyethyl methacrylate (manufactured by Wako Pure Chemical Industries), and MAA represents And methacrylic acid (manufactured by Wako Pure Chemical Industries).
The synthesis method of tetrahydrofuran-2-yl methacrylate (MATHF) is as follows.

[Synthesis of MATHF]
Methacrylic acid (86 g, 1 mol) was cooled to 15 ° C., and camphorsulfonic acid (4.6 g, 0.02 mol) was added. To the solution, 2-dihydrofuran (71 g, 1 mol, 1.0 equivalent) was added dropwise. After stirring for 1 hour, saturated sodium hydrogen carbonate (500 mL) was added, extracted with ethyl acetate (500 mL), dried over magnesium sulfate, filtered to insoluble matter and concentrated under reduced pressure at 40 ° C. or lower to give a yellow oily residue. Distillation under reduced pressure gave 125 g of tetrahydrofuran-2-yl methacrylate (MATHF) as a colorless oily substance (yield 80%) at a boiling point (bp.) Of 54 to 56 ° C./3.5 mmHg.

(1) Preparation of photosensitive composition After mixing each component shown in the following table to make a uniform solution, it was filtered using a polytetrafluoroethylene filter having a pore size of 0.1 μm, and Examples, References Solutions of the photosensitive compositions of Examples and Comparative Examples were respectively prepared.
Further, Comparative Example 12, Comparative Example 13, and Comparative Example 14 are the implementation of Example 1 of JP 2004-264623 A, Example 1 of JP 2009-258723 A, and JP 2010-26460 A, respectively. The resin described in the examples was used as a crosslinking agent, and the others were performed in the same manner as described above. In Comparative Examples 15 and 16, the photosensitive resin compositions described in Example 1 of JP-A No. 2001-194791 and Example 1 of JP-A No. 10-186664 were used, respectively.

B-1: Photoacid generator, manufactured by Ciba Japan, the following compound

B-2: Photoacid generator, manufactured by Midori Chemical, the following compound

B-3: Photoacid generator, 2- (4-methoxy-β-styryl) -bis (4,6-trichloromethyl) -s-triazine

N-1: sensitizer, manufactured by Kawasaki Kasei Kogyo, the following compound

G-1: Basic compound, 1,5-diazabicyclo [4.3.0] -5-nonene G-2: Basic compound, triphenylimidazole

W-1: Surfactant, the following compound

C-1: Epoxy resin, manufactured by DIC, EPICLON EXA-4822
C-2: Epoxy resin, manufactured by DIC, EPICLON EXA-4850
C-3: Epoxy resin, manufactured by DIC, EPICLON EXA-4816
C-4: Epoxy resin, manufactured by DIC, the following compound
C-5: Epoxy resin, manufactured by DIC, the following compound
C-6: poly d Chirenguriko - diglycidyl - ether n ≒ 9, made by NOF Epio - Le E-400
C-7: Epoxy resin, No. 61 of Example 1 of JP-A 61-0148224. Three compounds were employed.
C-8: Example 2 of JP-A-5-65331 Epoxy resin “B”
C-9: Example 2 of JP-A-5-65331 Epoxy resin “C”
C-10: Epoxy resin, manufactured by Mitsubishi Chemical Corporation, JER1004, the following compound
C-11: Epoxy resin, manufactured by Mitsubishi Chemical, JER157S65, the following compound
C-12: Epoxy resin, manufactured by DIC, EPICLON HP-4700, the following compound
C-13: Epoxy resin, Nippon Kayaku, NC-7000L, the following compound

Evaluation of sensitivity Each of the photosensitive composition solutions of Examples, Reference Examples and Comparative Examples was spin-coated on a silicon wafer having a silicon oxide film, and then pre-baked on a hot plate at 90 ° C. for 120 seconds to have a film thickness of 3 μm. A coating film was formed.
Next, it exposed through the predetermined | prescribed mask using i line | wire stepper (Canon Co., Ltd. product FPA-3000i5 +). One minute after the exposure, PEB was performed at 80 ° C. for 60 seconds on a hot plate.
Thereafter, the film was developed with a 0.4% aqueous solution of tetramethylammonium hydroxide at 23 ° C. for 60 seconds and rinsed with ultrapure water for 45 seconds. By these operations, the optimum exposure amount (Eopt) when resolving 10 μm line and space at 1: 1 was defined as sensitivity. The sensitivity can be said to be high when the exposure dose is lower than 70 mJ / cm ² . The evaluation results are shown in the following table.

Evaluation of elongation at break After spin coating each of the solutions of the photosensitive compositions of Examples, Reference Examples and Comparative Examples on a silicon wafer having a silicon oxide film, it was pre-baked on a hot plate at 90 ° C. for 120 seconds to have a film thickness of 10 μm. The coating film was formed.
Next, the entire surface was exposed at 300 mj / cm @ 2 using an i-line stepper (FPA-3000i5 + manufactured by Canon Inc.). Further, this sample was baked under the conditions shown in the table.
The sample was immersed in a 1% HF aqueous solution at room temperature for about 5 hours, the silicon oxide film was dissolved in the HF aqueous solution, and only the cured film was taken out. The cured film was washed with water and dried after HF was washed away with a saturated aqueous solution of Ca (OH) 2.
The cured film thus obtained was cut into a width of 5 mm and a length of 30 mm, and a tensile test was performed at room temperature with a tensile speed of 5 mm / min using Tensilon (RTM-50 Orientec). Was measured.

Evaluation of 5% thermogravimetric loss temperature A cured film was prepared in the same manner as the sample preparation for breaking elongation measurement. The cured film was heated from room temperature to 450 ° C. using TGA (manufactured by EXSTAR6000 SII) at a temperature rising rate of 10 ° C./min, and the temperature at which 5% weight loss from the initial weight was read.

  A semiconductor rewiring material is required to have heat resistance and toughness of a cured film. Conventionally, various resist materials mainly composed of heat-resistant polymers such as polyimide (PI) and polybenzoxazole (PBO) have excellent heat resistance and toughness, but generally require a high temperature of 350 ° C or higher for curing. In some cases, damage was given to the lower layer formed so far. However, this point is avoided in the present invention. That is, it has been found that the chemically amplified photosensitive composition of the present invention has high sensitivity, can be cured at low temperature, has sufficient heat resistance, and has a tough film quality. In addition, it has become possible to create with inexpensive materials.

13 Insulating layer 14 Surface protective film layer 15 Pad portion 16 Redistribution layer 17 Conductive ball 19 Cover coat layer 20 Barrier metal 23 Silicon chip 24 Connection portion

Claims (9)

(A) a compound whose alkali solubility is increased by an acid, (B) a compound which generates an acid upon irradiation with actinic rays and / or radiation, (C) a crosslinking agent, and the (C) crosslinking agent is represented by the following formula ( III): A chemically amplified positive photosensitive composition represented.
Formula (III)
(In formula (III), R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and X and Y each independently represent a divalent organic group. N is an integer of 0 to 20. ) The chemistry according to claim 1 , wherein (A) the compound whose alkali solubility is increased by an acid is a polymer containing a structural unit derived from (meth) acrylic acid or an ester thereof having a structure of the following general formula (I): Amplified positive photosensitive composition.
(In general formula (I), R ¹ and R ² each independently represent a hydrogen atom, a linear or branched alkyl group or a cycloalkyl group, provided that at least one of R ¹ and R ² is Represents an alkyl group or a cycloalkyl group, R ³ represents a linear or branched alkyl group, a cycloalkyl group, or an aralkyl group, and R ¹ or R ² and R ³ are linked to form a cyclic ether. You may do it.) (B) The chemically amplified positive photosensitive composition according to claim 1 or 2, wherein the compound capable of generating an acid upon irradiation with actinic rays and / or radiation is an oxime sulfonate compound. X and Y in the formula (III) are ethyleneoxyethyl group, di (ethyleneoxy) ethyl group, tri (ethyleneoxy) ethyl group, tetra (ethyleneoxy) ethyl group, propyleneoxypropyl group, di (propylene), respectively. Oxy) propyl group, tri (propyleneoxy) propyl group, tetra (propyleneoxy) propyl group, butyleneoxybutyl group, di (butyleneoxy) butyl group, tri (butyleneoxy) butyl group, tetra (butyleneoxy) butyl group, The chemically amplified positive according to any one of claims 1 to 3 , which is selected from an alkylene group having 2 to 15 carbon atoms and an aliphatic hydrocarbon group having 6 to 17 carbon atoms having a cycloalkane skeleton. Photosensitive composition. N in said Formula (III) is 1-10, The chemical amplification type positive photosensitive composition of any one of Claims 1-4 . The chemical amplification type positive according to any one of claims 1 to 5 , comprising (C) a crosslinking agent in a proportion of 10 to 80 parts by weight with respect to 100 parts by weight of the compound (A) whose alkali solubility is increased by an acid. Photosensitive composition. The chemically amplified positive photosensitive composition according to any one of claims 1 to 6 , which is used for forming a rewiring of a semiconductor. (1) applying a chemically amplified positive photosensitive composition according to the substrate to any one of claims 1 to 7
(2) a step of removing the solvent from the applied chemically amplified positive photosensitive composition;
(3) a step of exposing the applied chemically amplified positive photosensitive composition with actinic rays;
(4) a step of developing the exposed chemically amplified positive photosensitive composition with an aqueous developer, and
(5) A step of thermally curing the developed chemically amplified positive photosensitive composition. A cured film formed by the method according to claim 8 .