JP6826327B2 - Positive photosensitive resin composition - Google Patents

Description

The present invention relates to a positive photosensitive resin composition and a cured film obtained from the composition.
More specifically, the present invention relates to a positive photosensitive resin composition capable of forming an image having high water repellency and oil repellency on the surface of the cured film, a cured film thereof, and various materials using the cured film. This positive photosensitive resin composition is particularly suitable for use as an interlayer insulating film in a liquid crystal display or an EL display, a light-shielding material compatible with an inkjet method, or a partition material.

Generally, in a display element such as a thin film transistor (TFT) type liquid crystal display element or an organic EL (electroluminescence) element, a patterned electrode protective film, a flattening film, an insulating film and the like are provided. As a material for forming these films, among the photosensitive resin compositions, the photosensitive resin composition is characterized by having a small number of steps for obtaining a required pattern shape and having sufficient flatness. , Has been widely used in the past.

The above-mentioned films have excellent process resistance such as heat resistance, solvent resistance, long-term firing resistance, and metal spatter resistance, have good adhesion to the substrate, and are suitable for the purpose of use. In addition to having a wide process margin capable of forming a pattern under various process conditions, it is required to have various characteristics such as high sensitivity and high transparency and little film unevenness after development. Therefore, from the viewpoint of such required characteristics, a resin containing a naphthoquinone diazide compound has been widely used as the above-mentioned photosensitive resin composition.

It has been proposed that these materials are thermally crosslinked and cured by adding an epoxy cross-linking agent or containing a carboxyl group and an epoxy group in an acrylic resin (Patent Documents 1 and 2). .. However, when such a resin is used, sufficient sensitivity cannot be obtained, which leads to a decrease in throughput during display manufacturing. In addition, the pattern shape is likely to change depending on the baking temperature during post-baking, and precise temperature control is required.

Further, in recent years, a full-color display substrate manufacturing technique using an inkjet in the manufacturing process of a display display element has been actively studied. For example, regarding the production of a color filter in a liquid crystal display element, light is blocked in a section (hereinafter referred to as a bank) that defines pre-patterned pixels as compared with the conventional printing method, electrodeposition method, dyeing method, or pigment dispersion method. A color filter formed of a photosensitive resin layer and dropping ink droplets into an opening surrounded by the bank and a method for producing the same have been proposed (Patent Document 3). Further, also in the organic EL display element, a method has been proposed in which a bank is prepared in advance and ink to be a light emitting layer is dropped in the same manner to produce an organic EL display element (Patent Document 4).
However, when the ink droplets surrounded by the bank are dropped by the inkjet method, the substrate is provided with a pro-ink property (hydrophilicity) to prevent the ink droplets from overflowing to the adjacent pixel beyond the bank, and the surface of the bank is covered with ink droplets. Needs to be water repellent.

In order to achieve the above objectives, it is proposed that the substrate can be made hydrophilic and the bank can be made water repellent by continuous plasma (ozone) treatment such as oxygen gas plasma treatment and fluorine gas plasma treatment. (Patent Document 5), but the process is complicated. Further, a proposal has been made in which a fluorine-based surfactant or a fluorine-based polymer is blended with a photosensitive organic thin film (Patent Document 6), but consideration is given to not only photosensitive but also coating film property such as compatibility and addition amount. Not only are there many points to be considered, but UV ozone treatment during the hydrophilic treatment of the substrate reduces the water repellency of the surface, which is not practical.

On the other hand, conventionally, there is Japanese Patent Application Laid-Open No. 2015-172742 (Patent Document 7) as a negative type liquid repellent bank. Further, as a positive type, there is Japanese Patent Application Laid-Open No. 2012-22860 (Patent Document 8).

Japanese Unexamined Patent Publication No. 2000-103937 Japanese Unexamined Patent Publication No. 4-352101 Japanese Unexamined Patent Publication No. 2000-187111 Japanese Unexamined Patent Publication No. 11-542270 Japanese Unexamined Patent Publication No. 2000-353594 Japanese Unexamined Patent Publication No. 10-197715 Japanese Unexamined Patent Publication No. 2015-172742 Japanese Unexamined Patent Publication No. 2012-22860

The present invention has been made in view of the above circumstances, and a problem to be solved thereof is used for a liquid crystal display element, an organic EL display element, etc., and a cured film is used even after treatment such as plasma treatment or UV ozone treatment. The purpose of the present invention is to form an image of a cured film having high water repellency and high oil repellency on the surface, insulating properties, and a small amount of residue. In particular, in the fabrication of a substrate using an inkjet, the purpose is to form an image of a cured film that can prevent ink droplets from overflowing to adjacent pixels beyond the bank.

As a result of diligent studies to achieve the above object, the present inventors have made at least one group selected from a fluoroalkyl group having 3 to 10 carbon atoms, a polyfluoroether group, a silyl ether group and a polysiloxane group, and a quinonediazide. The present invention has been completed by finding that water repellency and liquid repellency can be efficiently imparted to the film surface by forming a cured film from a composition containing a polymer having a group.

That is, the present invention relates to the following.
1. 1. A thermosetting positive photosensitive resin composition containing the following component (A), component (B), component (C) and solvent (D).
Component (A): Polymer having a liquid-repellent group and a quinonediazide group,
(B) Ingredient: Alkali-soluble resin,
(C) Ingredient: 1,2-quinonediazide compound,
(D) Solvent.
2. 2. The positive photosensitive resin composition according to 1 above, which further satisfies at least one of the following (Z1) and (Z2).
(Z1): Further contains a cross-linking agent which is a component (E).
(Z2): A group in which the alkali-soluble resin of the component (B) further has a self-crosslinkable group or reacts with at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group and an amino group. Have more.
3. 3. 4. The above 1 or 2 wherein the liquid-repellent group of the component (A) is at least one group selected from a fluoroalkyl group having 3 to 10 carbon atoms, a polyfluoroether group, a silyl ether group and a polysiloxane group. Positive type photosensitive resin composition.
4. The positive photosensitive resin composition according to any one of 1 to 3 above, wherein the polymer of the component (A) is an acrylic polymer.
5. The positive photosensitive resin composition according to 4 above, wherein the acrylic polymer of the component (A) has a number average molecular weight of 2,000 to 100,000 in terms of polystyrene.
6. The positive photosensitive resin composition according to 4 or 5 above, wherein the acrylic polymer of the component (A) further has a group selected from a carboxyl group and a phenolic hydroxyl group.
7. The positive photosensitive resin composition according to any one of 1 to 6 above, wherein the alkali-soluble resin as the component (B) has a number average molecular weight of 2,000 to 50,000 in terms of polystyrene.
8. (B) The positive photosensitive resin composition according to any one of 1 to 7 above, which contains 0.1 to 20 parts by mass of the component (A) with respect to 100 parts by mass of the component.
9. The positive photosensitive member according to any one of 1 to 8 above, wherein the component (C) is 5 to 100 parts by mass with respect to 100 parts by mass of the total of the component (A) and the component (B). Sex resin composition.
10. The positive photosensitive member according to any one of 1 to 9 above, wherein the component (E) is 1 to 50 parts by mass with respect to a total of 100 parts by mass of the component (A) and the component (B). Sex resin composition.
11. The above 1 to 10 which further contains an antifoaming agent as a component (F) in an amount of 0.01 to 1.0 mass with respect to a total of 100 parts by mass of the component (A) and the component (B). Positive type photosensitive resin composition.
12. A cured film obtained by using the positive photosensitive resin composition according to any one of 1 to 11 above.
13. The display element having the cured film according to the above 12.
14. A display element having the cured film according to 12 above as an image forming underlayer film.

The positive photosensitive resin composition of the present invention can form a pattern with high sensitivity while maintaining the adhesion during development, and can form a cured film with a small amount of pattern residue.

The photosensitive resin composition of the present invention is a positive photosensitive resin composition containing the following components (A), (B), (C) and (D) solvent.
Component (A): Polymer having a liquid-repellent group and a quinonediazide group,
(B) Ingredient: Alkali-soluble resin;
(C) Ingredient: 1,2-quinonediazide compound,
(D) Solvent.

The photosensitive resin composition of the present invention preferably further satisfies at least one of the following (Z1) and (Z2).
(Z1): Further contains a cross-linking agent which is a component (E).
(Z2): A group in which the alkali-soluble resin of the component (B) further has a self-crosslinkable group or reacts with at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group and an amino group. Have more.

The details of each component will be described below.
<Ingredient (A)>
The component (A) is a polymer having a liquid-repellent group and a quinonediazide group.
In the present invention, examples of the polymer include polyimide, polyamic acid, polyamide, polyurea, polyurethane, phenol resin, epoxy resin, polysiloxane, polyester and acrylic polymer, and preferred polymers include acrylic polymers. Can be mentioned.
Here, the acrylic polymer is obtained by using a polymerizable unsaturated group such as an acrylic acid ester, a methacrylate ester, styrene, or maleimide, that is, a monomer having a polymerizable group containing a C = C double bond in the structure. Refers to the polymer to be produced.

Examples of polyamic acid, polyimide, polyamide, and polyurea include polyamic acid obtained by reacting diamine with an acid dianhydride, polyimide obtained by imidizing the polyamic acid, and polyamide or diamine obtained by reacting diamine with a dicarboxylic acid anhydride. A polymer obtained by reacting the above with a diamine and obtained from a monomer mixture containing at least one monomer having a fluoroalkyl group or a fluoroalkoxy group and at least one monomer having a hydroxy group, which will be described later. Examples thereof include a polymer in which a quinonediazide group has been introduced by the method.

Examples of the polyurethane include a polymer obtained by reacting a diol having a fluoroalkyl group or a fluoroalkoxy group with a diol having an amino group with a diisocyanate, and a quinone diazide group introduced by a method described later.

Examples of the phenol resin include a novolak resin obtained by polymerizing formaldehyde with a phenol having a fluoroalkyl group or a fluoroalkoxy group, and a polymer in which a quinonediazide group is introduced by a method described later.

The epoxy resin is an epoxy resin obtained by reacting bisphenol A and / or bisphenol F having a fluoroalkyl group or fluoroalkoxy group with glycidyl ether at the time of the bisphenol A and / or bisphenol F, and quinonediazide by the method described below. Examples include a polymer having a group introduced therein.

As the polysiloxane, a silane monomer mixture containing a trialkoxysilane having a fluoroalkyl group or a dialkoxysilanesilane having a fluoroalkyl group and a trialkoxysilane having an amino group or a dialkoxysilane having an amino group is polymerized. Examples of the obtained polymer include a polymer in which a quinonediazide group has been introduced by a method described later.

Examples of the polyester include a polymer obtained by reacting a dicarboxylic acid or tetracarboxylic dianhydride with a diol having a fluoroalkyl group or a fluoroalkoxy group, and a quinonediazide group introduced by a method described below.

<Introduction of liquid repellent group>
Examples of the liquid-repellent group include at least one group selected from a fluoroalkyl group having 3 to 10 carbon atoms, a polyfluoroether group, a silyl ether group and a polysiloxane group.

The fluoroalkyl group has 3 to 10 carbon atoms, and preferably a fluoroalkyl group having 4 to 10 carbon atoms.
Examples of such fluoroalkyl groups include 2,2,2-trifluoroethyl group, 2,2,3,3,3-pentafluoropropyl group, 2- (perfluorobutyl) ethyl group, and 3-perfluorobutyl group. -2-Hydroxypropyl group, 2- (perfluorohexyl) ethyl group, 3-perfluorohexyl-2-hydroxypropyl group, 2- (perfluorooctyl) ethyl group, 3-perfluorooctyl-2-hydroxypropyl group , 2- (Perfluorodecyl) ethyl group, 2- (perfluoro-3-methylbutyl) ethyl group, 3- (perfluoro-3-methylbutyl) -2-hydroxypropyl group, 2- (perfluoro-5-methyl) Hexyl) ethyl group, 2- (perfluoro-5-methylhexyl) -2-hydroxypropyl group, 2- (perfluoro-7-methyloctyl) ethyl group, and 2- (perfluoro-7-methyloctyl)- 2-Hydroxypropyl group, etc. may be mentioned.

In order to introduce a fluoroalkyl group having 3 to 10 carbon atoms into the polymer which is the component (A) of the present invention, a monomer having a fluoroalkyl group having 3 to 10 carbon atoms may be copolymerized.

Specific examples of the monomer having a fluoroalkyl group having 3 to 10 carbon atoms when the component (A) is an acrylic polymer include 2,2,2-trifluoroethyl acrylate and 2,2,2-tri. Fluoroethyl methacrylate, 2,2,3,3,3-pentafluoropropyl acrylate, 2,2,3,3,3-pentafluoropropyl methacrylate, 2- (perfluorobutyl) ethyl acrylate, 2- (perfluorobutyl) ) Ethyl methacrylate, 3-perfluorobutyl-2-hydroxypropyl acrylate, 3-perfluorobutyl-2-hydroxypropyl methacrylate, 2- (perfluorohexyl) ethyl acrylate, 2- (perfluorohexyl) ethyl methacrylate, 3- Perfluorohexyl-2-hydroxypropyl acrylate, 3-perfluorohexyl-2-hydroxypropyl methacrylate, 2- (perfluorooctyl) ethyl acrylate, 2- (perfluorooctyl) ethyl methacrylate, 3-perfluorooctyl-2- Hydroxypropyl acrylate, 3-perfluorooctyl-2-hydroxypropyl methacrylate, 2- (perfluorodecyl) ethyl acrylate, 2- (perfluorodecyl) ethyl methacrylate, 2- (perfluoro-3-methylbutyl) ethyl acrylate, 2 -(Perfluoro-3-methylbutyl) ethyl methacrylate, 3- (perfluoro-3-methylbutyl) -2-hydroxypropyl acrylate, 3- (perfluoro-3-methylbutyl) -2-hydroxypropyl methacrylate, 2- (per) Fluoro-5-methylhexyl ethyl acrylate, 2- (perfluoro-5-methylhexyl) ethyl methacrylate, 2- (perfluoro-5-methylhexyl) -2-hydroxypropyl acrylate, 2- (perfluoro-5-) Methylhexyl) -2-hydroxypropyl methacrylate, 2- (perfluoro-7-methyloctyl) ethyl acrylate, 2- (perfluoro-7-methyloctyl) ethyl methacrylate, 2- (perfluoro-7-methyloctyl)- Examples thereof include 2-hydroxypropyl acrylate and 2- (perfluoro-7-methyloctyl) -2-hydroxypropyl methacrylate.

Examples of the polyfluoroether group include an Rf group (a) having a polyfluoroether structure represented by the following formula 1.
− (X−O) _n− Y ・ ・ ・ Equation 1
In formula 1, X is a divalent saturated hydrocarbon group having 1 to 10 carbon atoms or a fluorolated divalent saturated hydrocarbon group having 1 to 10 carbon atoms, and is the same for each unit enclosed by n. Indicates a group or a different group, where Y is a hydrogen atom (only when a fluorine atom is not bonded to a carbon atom adjacent to an oxygen atom adjacent to Y), a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms. It represents a fluorosaturated monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and n represents an integer of 2 to 50. However, the total number of fluorine atoms in Equation 1 is 2 or more.

As an aspect of X and Y in the formula 1, preferably, X is an alkylene group fluorosylated except for one hydrogen atom having 1 to 10 carbon atoms or a perfluorolated alkylene group having 1 to 10 carbon atoms. It indicates the same group or a different group for each unit enclosed by n, and Y is an alkyl group or a par having 1 to 20 carbon atoms which is fluorolated except for one hydrogen atom having 1 to 20 carbon atoms. Those showing a fluorolated alkyl group can be mentioned.

More preferably, X is a perfluorolated alkylene group having 1 to 10 carbon atoms, and indicates the same group or a different group for each unit enclosed by n, as an embodiment of X and Y in the formula 1. , Y represents a perfluorolated alkyl group having 1 to 20 carbon atoms.

In Equation 1, n represents an integer of 2 to 50. n is preferably 2 to 30, more preferably 2 to 15. When n is 2 or more, the liquid repellency is good. When n is 50 or less, the polymer which is the component (A) is synthesized by copolymerizing a monomer having an Rf group (a) with a monomer having a quinonediazide group, a phenolic hydroxyl group or a carboxyl group, or another monomer. When this is done, the compatibility of the monomers becomes good.

The total number of carbon atoms in the Rf group (a) having the polyfluoroether structure represented by the formula 1 is preferably 2 to 50, more preferably 2 to 30. In this range, the polymer which is the component (A) exhibits good liquid repellency. Further, when the polymer as the component (A) is synthesized by copolymerizing a monomer having an Rf group (a) with a monomer having a quinonediazide group, a phenolic hydroxyl group or a carboxyl group, or another monomer, the monomer is used. Good compatibility.

Examples of _{X, -CF 2 -, - CF} 2 CF 2 -, - CF 2 CF 2 CF 2 -, - CF 2 CF (CF 3) -, - CF 2 CF 2 CF 2 CF 2 -, - CF ₂ CF ₂ CF (CF ₃ )-and CF ₂ CF (CF ₃ ) CF _2- .

Specific examples of Y include −CF ₃ , −CF ₂ CF ₃ , −CF ₂ CHF ₂ , − (CF ₂ ) ₂ CF ₃ , − (CF ₂ ) ₃ CF ₃ , − (CF ₂ ) ₄ CF ₃ , − (CF ₂ ) ₅ CF ₃ , − (CF ₂ ) ₆ CF ₃ , − (CF ₂ ) ₇ CF ₃ , − (CF ₂ ) ₈ CF ₃ , − (CF ₂ ) ₉ CF ₃ , and (CF ₂ ) ₁₁ CF ₃ , − (CF ₂ ) ₁₅ CF ₃ can be mentioned.

A preferred embodiment of the Rf group (a) having a polyfluoroether structure represented by the formula 1 is the Rf group (a) represented by the formula 2.

−C _p-1 F _{2 (p-1)} −O− (C _p F _2p −O) _n-1 −C _q F _{2q + 1}・ ・ ・ Equation 2
In Equation 2, p represents an integer of 2 or 3, and each unit enclosed by n has the same group, q represents an integer of 1 to 20, and n represents an integer of 2 to 50.

Specifically, as the Rf group (a) represented by the formula 2,
−CF ₂ O (CF ₂ CF ₂ O) _n-1 CF ₃ (n is 2-9),
−CF (CF ₃ ) O (CF ₂ CF (CF ₃ ) O) _n-1 C ₆ F ₁₃ (n is 2 to 6),
−CF (CF ₃ ) O (CF ₂ CF (CF ₃ ) O) _n-1 C ₃ F ₇ (n is 2 to 6)
Is preferably mentioned from the viewpoint of ease of synthesis.

The Rf groups (a) in the polymer as the component (A) may all be the same or different.

The silyl ether group means a group in which the hydroxy group of the alcohol is protected by a trialkylsilyl group, and is preferably a group represented by the following formula.
−X ⁴ −Si (O−SiX ¹ X ² X ³ ) ₃
(In the formula, X ¹ , X ² , and X ³ independently represent an alkyl group having 1 to 3 carbon atoms, and X ⁴ represents an alkylene group having 1 to 6 carbon atoms.)

In order to introduce a silyl ether group into the polymer which is the component (A) of the present invention, a monomer having a silyl ether group may be copolymerized.

Examples of the monomer having a silyl ether group when the component (A) is an acrylic polymer include methacryloxypropyltris (trimethylsiloxy) silane, methacryloxytrispropylsilane, 2- (methacryloxyethoxy) trimethylsilane, and 2-(. Examples thereof include methacryloxyethyl) trimethylsilane, 2- (acryloxyethoxy) trimethylsilane, acrylicoxytrispropylsilane, 2- (acryloxyethyl) trimethylsilane, and acrylicoxypropyltris (trimethylsiloxy) silane.

Examples of the polysiloxane group include a group (a) having a polysiloxane structure represented by the formula 3. Hereinafter, the group (a) having a polysiloxane structure represented by the formula 3 is referred to as a pSi group (a).
^{- (SiR 1 R 2 -O)} n -SiR 1 R 2 R 3 ··· Equation 3
(However, R ¹ and R ² independently represent hydrogen, an alkyl group, a cycloalkyl group or an aryl group, R ³ represents hydrogen or an organic group having 1 to 10 carbon atoms, and n represents an integer of 1 to 200. .).

R ¹ and R ² independently represent hydrogen, an alkyl group, a cycloalkyl group or an aryl group, and may be the same or different for each syroxy unit. Since the polymer (A) has good liquid repellency, R ¹ and R ² are preferably hydrogen, methyl or phenyl groups, and all syroxy units R ¹ and R ^{2 are used.} Is preferably a methyl group. Further, R ³ may contain a nitrogen atom, an oxygen atom and the like.

Examples of the method for introducing the pSi group (a) into the polymer (A) are a method of copolymerizing a monomer having a pSi group (a) and a compound having a pSi group (a) in a polymer having a reaction site. Examples thereof include various modification methods for reacting with, a method using a polymerization initiator having a pSi group (a), and the like.

Examples of the monomer having a pSi group (a) include CH ₂ = CHCOO (pSi) and CH ₂ = C (CH ₃ ) COO (pSi). However, pSi represents the pSi group (a). The monomer having the pSi group (a) may be used alone or in combination of two or more.

Examples of various modification methods for reacting a polymer having a reaction site with a compound having a pSi group (a) include the following methods.

A method in which a monomer having an epoxy group is copolymerized in advance, and then a compound having a carboxyl group at one end and a pSi group at one end is reacted. A method in which a monomer having an epoxy group is copolymerized in advance, and then a compound having an amino group at one end and a pSi group at one end is reacted. A method in which a monomer having an epoxy group is copolymerized in advance, and then a compound having a mercapto group at one end and a pSi group at one end is reacted. A method in which a monomer having an amino group is copolymerized in advance, and then a compound having a carboxyl group at one end and a pSi group at one end is reacted.

A method in which a monomer having an amino group is copolymerized in advance, and then a compound having an epoxy group at one end and a pSi group at one end is reacted. A method in which a monomer having a carboxyl group is copolymerized in advance, and then a compound having an epoxy group at one end and a pSi group at one end is reacted. A method in which a monomer having a carboxyl group is copolymerized in advance, and then a compound having an amino group at one end and a pSi group at one end is reacted. A method in which a monomer having a carboxyl group is copolymerized in advance, and then a compound having a silyl chloride group at one end and a pSi group at one end is reacted. A method in which a monomer having a hydroxyl group is copolymerized in advance, and then a compound having a silyl chloride group at one end and a PSi group at one end is reacted.

The polymerization initiator having a pSi group (a) may contain a group having a divalent polysiloxane structure in the main chain of the initiator molecule, or may be monovalent in the terminal portion or side chain of the initiator molecule. It may contain a group having a polysiloxane structure of. Initiator Examples of the initiator in which a group having a divalent polysiloxane structure is contained in the molecular main chain include a compound having a group having a divalent polysiloxane structure and an azo group alternately. Examples of commercially available products include VPS-1001 and VPS-0501 (all manufactured by Wako Pure Chemical Industries, Ltd.).

<Introduction of quinonediazide group>
Specifically, the quinone diazide group is a 1,2-naphthoquinone-2-diazide-5-sulfonyl group.

In order to introduce a quinonediazide group into the polymer (A), a monomer having a phenolic hydroxyl group or a monomer having an amino group is esterified or amidated with 1,2-quinonediazide sulfonic acid to use a monomer obtained together. Examples include a method of polymerizing. Further, as a method for introducing a quinonediazide group into the polymer which is the component (A) of the present invention, a monomer having a phenolic hydroxyl group or a monomer having an amino group is copolymerized, and then the phenolic hydroxyl group of the obtained resin is obtained. Alternatively, the amino group may be esterified or amidated with 1,2-quinonediazide sulfonic acid.

Examples of the monomer having a phenolic hydroxyl group and a polymerizable unsaturated group when the component (A) is an acrylic polymer include p-hydroxystyrene, α-methyl-p-hydroxystyrene, N-hydroxyphenylmaleimide, and the like. Examples thereof include N-hydroxyphenylacrylamide, N-hydroxyphenylmethacrylate, p-hydroxyphenylacrylate, p-hydroxyphenylmethacrylate and the like, and these can be used alone or in combination of two or more. Of these, a monomer selected from p-hydroxyphenyl acrylate and p-hydroxyphenyl methacrylate is preferable.

When 1.05 to 1.2 equivalents of 1,2-quinonediazide sulfonic acid chloride are reacted in a solvent with 1 equivalent of the monomer having a phenolic hydroxyl group and a polymerizable unsaturated group, the monomer is polymerizable with the phenolic hydroxyl group. A monomer having an unsaturated group can be obtained.

The polymer as the component (A) preferably further has a group selected from a carboxyl group and a phenolic hydroxyl group in that it is easy to develop. For a polymer having a group further selected from a carboxyl group and a phenolic hydroxyl group, a repeating unit having a group selected from a carboxyl group and a phenolic hydroxyl group may be introduced into the component (A), and these repeating units may be used as the component (A). At least one of the monomer having a phenolic hydroxyl group and a polymerizable unsaturated group and the monomer having a carboxyl group may be copolymerized. Further, when introducing a quinonediazide group into the polymer which is the component (A), 1,2-quinonediazide sulfonic acid may be reacted in a number of moles smaller than the number of moles of the phenolic hydroxyl group.

Examples of the monomer having a carboxyl group when the component (A) is an acrylic polymer include acrylic acid, methacrylic acid, crotonic acid, mono- (2- (acryloyloxy) ethyl) phthalate, and mono- (2-( Examples thereof include methacryloyloxy) ethyl) phthalate, N- (carboxyphenyl) maleimide, N- (carboxyphenyl) methacrylicamide, and N- (carboxyphenyl) acrylamide.

In the polymer of the component (A), the amount of the liquid-repellent group introduced is preferably 5 to 60 mol% with respect to all the repeating units. If it is less than 5 mol%, it may not have a liquid-repellent effect. If it is more than 60 mol%, problems such as aggregation may occur.

In the polymer of the component (A), the amount of the quinonediazide group introduced is preferably 5 to 95 mol% with respect to all the repeating units. If it is less than 5 mol%, there may be a problem in developability. If it is more than 95 mol%, the liquid-repellent repeating unit will be too small.

When the polymer of the component (A) further has a repeating unit having a group selected from a carboxyl group and a phenolic hydroxyl group, the amount to be introduced is preferably 1 to 30 mol% with respect to all the repeating units. If it is more than 30 mol%, it may affect the developability.

The number average molecular weight of the polymer of the component (A) is preferably 2,000 to 100,000. It is more preferably 3,000 to 50,000, still more preferably 4,000 to 25,000. If the number average molecular weight is greater than 100,000, residues may occur.

When the component (A) is an acrylic polymer, the method for producing the polymer of the component (A) is as follows: a monomer having a liquid-repellent group, for example, a monomer having a fluoroalkyl group having 3 to 10 carbon atoms. A monomer having a polyfluoroether group, at least one of a monomer having a silyl ether group and a monomer having a polysiloxane group, and a monomer having a phenolic hydroxyl group and a polymerizable unsaturated group are esterified with 1,2-quinonediazide sulfonic acid. A polymerization reaction of a monomer obtained by polymerization or amidation and, if desired, a monomer other than the above (hereinafter, also referred to as monomer A) in a solvent in the presence of a polymerization initiator at a temperature of 50 to 110 ° C. Obtained by At that time, the solvent used is not particularly limited as long as it dissolves the monomer constituting the alkali-soluble polymer and the polymer having a specific functional group. Specific examples include the solvent described in (D) Solvent described later.

The other monomer A is preferably a monomer having no alkali-soluble group (hydroxyphenyl group, carboxyl group).
Specific examples of such other monomer A include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, glycidyl methacrylate, cyclohexyl methacrylate, and isobornyl methacrylate. Methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, 2-aminomethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, γ-butyrolactone methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tri Cyclodecyl methacrylate, 8-ethyl-8-tricyclodecyl methacrylate, methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, glycidyl acrylate, cyclohexyl acrylate, isobol Nyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, 2-aminomethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, γ-butyrolactone acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl- Examples thereof include 8-tricyclodecyl acrylate, 8-ethyl-8-tricyclodecyl acrylate, styrene, vinylnaphthalene, vinylanthracene, vinyl biphenyl and the like.

The polymer having a specific functional group thus obtained is usually in the state of a solution dissolved in a solvent.

Further, the solution of the specific copolymer obtained as described above is added under stirring with diethyl ether, water or the like to reprecipitate, and the generated precipitate is filtered and washed, and then under normal pressure or reduced pressure. Then, the powder of the specific copolymer can be obtained by drying at room temperature or by heating. By such an operation, the polymerization initiator and the unreacted monomer coexisting with the specific copolymer can be removed, and as a result, the purified powder of the specific copolymer can be obtained. If the powder cannot be sufficiently purified by one operation, the obtained powder may be redissolved in a solvent and the above operation may be repeated.
In the present invention, the powder of the specific copolymer may be used as it is, or the powder may be redissolved in, for example, the solvent (D) described later and used as a solution.

Further, in the present invention, the polymer of the component (A) may be a mixture of a plurality of specific copolymers.

<Ingredient (B)>
The component (B) of the present invention is a resin having an alkali-soluble group. Examples of the alkali-soluble group include a phenolic hydroxy group, a carboxyl group, an acid anhydride group, an imide group, a sulfonyl group, a phosphoric acid, a boric acid and a group represented by the following formula (b1).
(In formula (b1), R represents an alkyl group, an alkoxy group or a phenyl group.)

In the above formula (b1), examples of the alkyl group represented by R ₅ include an alkyl group having 1 to 20 carbon atoms, and an alkyl group having 1 to 5 carbon atoms is preferable.
Examples of such alkyl groups include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group and n-pentyl group. , 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-Dimethyl-n-propyl group, 1-ethyl-n-propyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group Group, 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl- n-Butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2 -Trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, n-heptyl Group, n-octyl group, n-nonyl group, n-decanyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl Examples thereof include a group, an n-octadecyl group, an n-nonadecil group, an n-eicosyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and a cycloheptyl group.
Among them, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an isobutyl group and the like are preferable.

In the above formula (b1), examples of the alkoxy group represented by R ₅ include an alkoxy group having 1 to 20 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms is preferable.
Examples of such an alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, an s-butoxy group, a t-butoxy group and an n-pentoxy group. , 1-Methyl-n-butoxy group, 2-methyl-n-butoxy group, 3-methyl-n-butoxy group, 1,1-dimethyl-n-propoxy group, 1,2-dimethyl-n-propoxy group, 2,2-Dimethyl-n-propoxy group, 1-ethyl-n-propoxy group, n-hexyloxy group, 1-methyl-n-pentyloxy group, 2-methyl-n-pentyloxy group, 3-methyl- n-pentyloxy group, 4-methyl-n-pentyloxy group, 1,1-dimethyl-n-butoxy group, 1,2-dimethyl-n-butoxy group, 1,3-dimethyl-n-butoxy group, 2 , 2-Dimethyl-n-butoxy group, 2,3-dimethyl-n-butoxy group, 3,3-dimethyl-n-butoxy group, 1-ethyl-n-butoxy group, 2-ethyl-n-butoxy group, 1,1,2-trimethyl-n-propoxy group, 1,2,2, -trimethyl-n-propoxy group, 1-ethyl-1-methyl-n-propoxy group, 1-ethyl-2-methyl-n- Propoxy group, n-heptyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, n-undecyloxy group, n-dodecyloxy group, n-tridecyloxy group, n-tetradecyloxy group Group, n-pentadecyloxy group, n-hexadecyloxy group, n-heptadecyloxy group, n-octadecyloxy group, n-nonadesyloxy group, n-eicosadeciloxy group, cyclopropoxy group, cyclobutoxy group, Cyclopentyloxy group, cyclohexyloxy group, cycloheptyloxy group and the like can be mentioned.
Among them, a methoxy group, an ethoxy group, an n-propoxy group and the like are preferable.

Examples of the group represented by the above formula (b1) include the following structures and the like.

Among the above alkali-soluble groups, an alkali-soluble resin having at least one organic group selected from the group consisting of a phenolic hydroxy group and a carboxyl group and having a number average molecular weight of 2,000 to 50,000. It is preferable to have.
The alkali-soluble resin of the component (B) may be any alkali-soluble resin having such a structure, and the type of the main chain skeleton and side chains of the polymer constituting the resin is not particularly limited.

However, the alkali-soluble resin of the component (B) has a number average molecular weight in the range of 2,000 to 50,000. If the number average molecular weight is more than 50,000 and is excessive, development residue is likely to be generated and the sensitivity is greatly lowered, while if the number average molecular weight is less than 2,000 and is too small, the development is carried out. At that time, a considerable amount of film loss may occur in the exposed area, resulting in insufficient curing.

Examples of the alkali-soluble resin of the component (B) include an acrylic resin, a polyhydroxystyrene resin, a polyimide precursor, and a polyimide.

Further, in the present invention, an alkali-soluble resin composed of a copolymer obtained by polymerizing a plurality of types of monomers (hereinafter referred to as a specific copolymer) can also be used as the component (B). In this case, the alkali-soluble resin of the component (B) may be a blend of a plurality of specific copolymers.

That is, the above-mentioned specific copolymer consists of a monomer that expresses alkali solubility, that is, a monomer having at least one selected from the group consisting of a phenolic hydroxy group and a carboxyl group, and a group of monomers copolymerizable with these monomers. It is a copolymer formed by using at least one selected monomer as an essential constituent unit, and has a number average molecular weight of 2,000 to 50,000. If the number average molecular weight is greater than 50,000, residues may occur.

The above-mentioned "monomer having at least one selected from the group consisting of a carboxyl group and a phenolic hydroxy group" has a monomer having a carboxyl group and a monomer having a phenolic hydroxy group, and further having these carboxyl groups and a phenolic hydroxy group. Contains monomers. These monomers are not limited to those having one carboxyl group or phenolic hydroxy group, and may have a plurality of these monomers.

Specific examples of the above-mentioned monomers will be given below, but the present invention is not limited thereto.
Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, mono- (2- (acryloyloxy) ethyl) phthalate, mono- (2- (methacryloyloxy) ethyl) phthalate, and N- (carboxyphenyl). ) Maleimide, N- (carboxyphenyl) methacrylamide, N- (carboxyphenyl) acrylamide and the like.

Examples of the monomer having a phenolic hydroxy group include hydroxystyrene, N- (hydroxyphenyl) acrylamide, N- (hydroxyphenyl) methacrylamide, N- (hydroxyphenyl) maleimide, 4-hydroxyphenyl methacrylate and the like.

Examples of the monomer copolymerizable with the monomer having at least one selected from the group consisting of a carboxyl group and a phenolic hydroxy group include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, and 5-acryloyloxy-6-hydroxy. Norbornen-2-carboxylic-6-lactone, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 5-methacryloyloxy-6-hydroxynorbornen-2-carboxylic-6-lactone, 2-aminoethyl acrylate, 2- Aminomethyl methacrylate and the like can be mentioned.

The ratio of the unsaturated carboxylic acid derivative and / or the monomer having a phenolic hydroxyl group and the polymerizable unsaturated group in the production of the alkali-soluble acrylic polymer of the component (B) is used in the production of the alkali-soluble acrylic polymer of the component (B). Of all the monomers used, it is preferably 10 to 90 mol%, more preferably 30 to 85 mol%, most preferably 50 to 80 mol%. When the unsaturated carboxylic acid derivative is less than 10% by weight, the alkali solubility of the polymer is insufficient.

The alkali-soluble resin, which is the component (B) of the present invention, is obtained by further copolymerizing a monomer having a hydroxyalkyl group and a polymerizable unsaturated group from the viewpoint of further stabilizing the pattern shape after curing. Is preferable.

Examples of the monomer having a hydroxyalkyl group and a polymerizable unsaturated group include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2,3-dihydroxypropyl acrylate, and 2-hydroxyethyl methacrylate. Examples thereof include 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl methacrylate, glycerin monomethacrylate, 5-acryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone and the like.

The ratio of the monomer having a hydroxyalkyl group and a polymerizable unsaturated group in the production of the alkali-soluble acrylic polymer of the component (B) is preferably 10 to 60% by weight, more preferably 5 to 50% by weight, and most preferably. Is 20-40% by weight. If the amount of the monomer having a hydroxyalkyl group and a polymerizable unsaturated group is less than 10% by weight, the effect of stabilizing the pattern shape of the copolymer may not be obtained. If it is 60% by weight or more, the alkali-soluble group of the component (B) may be insufficient, and the properties such as developability may be deteriorated.

The alkali-soluble resin which is the component (B) of the present invention is preferably one obtained by further copolymerizing an N-substituted maleimide compound from the viewpoint of increasing the Tg of the copolymer.

N-substituted maleimide compounds Examples of maleimide compounds include N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide. From the viewpoint of transparency, those having no aromatic ring are preferable, those having an alicyclic skeleton are more preferable from the viewpoint of developability, transparency and heat resistance, and cyclohexylmaleimide is most preferable.

The ratio of the N-substituted maleimide in the production of the alkali-soluble acrylic polymer of the component (B) is preferably 10 to 60% by weight, more preferably 5 to 50% by weight, and most preferably 20 to 40% by weight. When the N-substituted maleimide is less than 10% by weight, the Tg of the copolymer becomes low, and the heat resistance may be inferior. If it is 60% by weight or more, the transparency may decrease.

When the positive photosensitive resin composition of the present invention satisfies the requirement (Z2), the alkali-soluble resin (B) used in the present invention further has a self-crosslinking group, or has a hydroxy group, a carboxyl group, or an amide. It is preferably a copolymer further having a group (hereinafter, also referred to as a crosslinkable group) that reacts with at least one group selected from the group consisting of a group and an amino group.

Examples of the self-crosslinking group include an N-alkoxymethyl group, an N-hydroxymethyl group and an alkoxysilyl group.
Examples of the crosslinkable group include an epoxy group, an oxetane group, a vinyl group, a blocked isocyanate group and the like.
When the self-crosslinkable group or the crosslinkable group is contained in the resin of the component (B), the content may be 0.1 to 0.9 per unit of the repeating unit in the resin of the component (B). Preferably, from the viewpoint of developability and solvent resistance, 0.1 to 0.8 is more preferable.

The alkali-soluble resin of the component (B) further contains a crosslinkable group such as an epoxy group, an oxetane group, a vinyl group and a blocked isocyanate group, and a self-crosslinkable group such as an N-alkoxymethyl group, an N-hydroxymethyl group and an alkoxysilyl group. When it has a repeating unit having at least one selected from, for example, it has a radically polymerizable group, a crosslinkable group such as an epoxy group, an oxetane group, a vinyl group and a blocked isocyanate group, and an N-alkoxymethyl group and N-hydroxy. An unsaturated compound having at least one selected from self-crosslinking groups such as a methyl group and an alkoxysilyl group may be copolymerized.

Here, as N of the N-alkoxymethyl group, that is, the nitrogen atom, the nitrogen atom of amide, the nitrogen atom of thioamide, the nitrogen atom of urea, the nitrogen atom of thiourea, the nitrogen atom of urethane, and the nitrogen atom of the nitrogen-containing heterocycle Examples include nitrogen atoms bonded to adjacent positions of. Therefore, the N-alkoxymethyl group includes nitrogen bonded to the nitrogen atom of amide, the nitrogen atom of thioamide, the nitrogen atom of urea, the nitrogen atom of thiourea, the nitrogen atom of urethane, and the nitrogen atom of the nitrogen-containing heterocycle. Examples thereof include a structure in which an alkoxymethyl group is bonded to a nitrogen atom selected from an atom or the like.

Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group and 1-methyl-n. -Butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl- n-propyl group, 1-ethyl-n-propyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group, 4-methyl- n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl-n-butyl group, 2 , 3-Dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl Group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, n-heptyl group, 1-methyl- n-hexyl group, 2-methyl-n-hexyl group, 3-methyl-n-hexyl group, 1,1-dimethyl-n-pentyl group, 1,2-dimethyl-n-pentyl group, 1,3-dimethyl -N-pentyl group, 2,2-dimethyl-n-pentyl group, 2,3-dimethyl-n-pentyl group, 3,3-dimethyl-n-pentyl group, 1-ethyl-n-pentyl group, 2- Ethyl-n-pentyl group, 3-ethyl-n-pentyl group, 1-methyl-1-ethyl-n-butyl group, 1-methyl-2-ethyl-n-butyl group, 1-ethyl-2-methyl- n-Butyl group, 2-methyl-2-ethyl-n-butyl group, 2-ethyl-3-methyl-n-butyl group, n-octyl group, 1-methyl-n-heptyl group, 2-methyl-n -Heptyl group, 3-methyl-n-heptyl group, 1,1-dimethyl-n-hexyl group, 1,2-dimethyl-n-hexyl group, 1,3-dimethyl-n-hexyl group, 2,2- Dimethyl-n-hexyl group, 2,3-dimethyl-n-hexyl group, 3,3-dimethyl-n-hexyl group, 1-ethyl-n-hexyl group, 2-ethyl-n-hexyl group, 3-ethyl -N-hexyl group, 1-methyl-1-ethyl-n-pentyl group, 1-methyl-2-ethyl-n-pentyl group, 1-methyl-3-ethyl-n-pentyl group, 2-methy Examples thereof include ru-2-ethyl-n-pentyl group, 2-methyl-3-ethyl-n-pentyl group, 3-methyl-3-ethyl-n-pentyl group, n-nonyl group, n-decyl group and the like. ..

Examples of unsaturated compounds having radical polymerizable properties and having an epoxy group include glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, and glycidyl α-n-butyl acrylate. , Acrylic acid-3,4-epoxybutyl, methacrylate-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylate-6,7-epoxyheptyl, α-ethylacrylic acid-6,7 -Epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether and the like can be mentioned. Of these, glycidyl methacrylate, -6,7-epoxyheptyl methacrylic acid, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3,4-epoxycyclohexyl methacrylate and the like. It is preferably used. These may be used alone or in combination.

Examples of the unsaturated compound having a radical polymerizable property and having an oxetane group include a (meth) acrylic acid ester having an oxetane group. Among such monomers, 3- (methacryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyl-oxetane, 3- (acryloyloxymethyl) -3- Ethyl-oxetan, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (acryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-phenyl-oxetan, 3- (Acryloyloxymethyl) -2-phenyl-oxetan, 2- (methacryloyloxymethyl) oxetane, 2- (acryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, 2- (acryloyloxymethyl) Methyl) -4-trifluoromethyloxetane is preferable, and 3- (methacryloyloxymethyl) -3-ethyl-oxetane, 3- (acryloyloxymethyl) -3-ethyl-oxetane and the like are preferably used.

Examples of unsaturated compounds having radical polymerizable properties and an N-alkoxymethyl group include N-butoxymethylacrylamide, N-isobutoxymethylacrylamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, and N-methylolacrylamide. And so on.

Examples of the monomer having a radical polymerizable property and further having a hydroxymethylamide group include N-hydroxymethylacrylamide and N-hydroxymethylmethacrylamide.

Examples of the monomer having a radical polymerizable property and further having a vinyl group include 1,2-epoxy-5-hexene and 1,7-octadienmonoepoxiside.

Examples of the monomer having a radical polymerizable property and a blocked isocyanate group include 2- (0- (1'-methylpropyridaneamino) carboxyamino) ethyl methacrylate and 2- (3,5-dimethylpyrazolyl) methacrylate. Carbonylamino) ethyl and the like can be mentioned.

Examples of the monomer having radical polymerization property and further having an alkoxysilyl group include 3-acryloyloxytrimethoxysilane, 3-acryloyloxytriethoxysilane, 3-methacryloyloxytrimethoxysilane, and 3-methacryloyloxytriethoxysilane. Can be mentioned.

It has radical polymerizable property and is selected from at least a crosslinkable group such as an epoxy group, an oxetane group, a vinyl group and a blocked isocyanate group and a self-crosslinkable group such as an N-alkoxymethyl group, an N-hydroxymethyl group and an alkoxysilyl group. Containing a structural unit derived from an unsaturated compound having one type, preferably 10 to 70% by weight, particularly preferably 20 to 60% by weight, based on the total of all the repeating units of the alkali-soluble resin (B). doing. When this structural unit is less than 10% by weight, the heat resistance and surface hardness of the obtained cured film tend to decrease, while when the amount of this structural unit exceeds 70% by weight, the radiation-sensitive resin composition is stored. Stability tends to decrease.

Further, in the present invention, the acrylic polymer of the component (B) may be a copolymer formed by a monomer other than the above-mentioned monomer (hereinafter, referred to as other monomer) as a constituent unit. Specifically, the other monomer may be a monomer copolymerizable with at least one selected from the group consisting of the above-mentioned monomer having a carboxyl group and the monomer having a phenolic hydroxy group, and the characteristics of the component (B) can be determined. It is not particularly limited as long as it does not impair. Specific examples of such monomers include acrylic acid ester compounds, methacrylic acid ester compounds, maleimides, acrylamide compounds, acrylonitrile, styrene compounds, vinyl compounds and the like.
Specific examples of the other monomers will be given below, but the present invention is not limited thereto.

Examples of the acrylic acid ester compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, glycidyl acrylate, and phenoxyethyl acrylate, 2,2,2-. Trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, 2-aminoethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxy Butyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, and 8-ethyl-8-tricyclodecyl acrylate, diethylene glycol monoacrylate, caprolactone. Examples thereof include 2- (acryloyloxy) ethyl ester and poly (ethylene glycol) ethyl ether acrylate.

Examples of the methacrylic acid ester compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, glycidyl methacrylate, phenoxyethyl methacrylate, 2,2,2-. Trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, 2-aminomethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxy Butyl methacrylate, 2-methyl-2-adamantyl methacrylate, γ-butyrolactone methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, and 8-ethyl-8-tricyclodecyl methacrylate, Examples thereof include diethylene glycol monomethacrylate, caprolactone 2- (methacryloyloxy) ethyl ester, and poly (ethylene glycol) ethyl ether methacrylate.

Examples of the acrylamide compound include N-methylacrylamide, N-methylmethacrylamide, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, and N-butoxy. Examples thereof include methyl acrylamide and N-butoxymethylmethacrylamide.

Examples of the vinyl compound include methyl vinyl ether, benzyl vinyl ether, cyclohexyl vinyl ether, vinylnaphthalene, vinylanthracene, vinylcarbazole, allylglycidyl ether, 3-ethenyl-7-oxabicyclo [4.1.0] heptane, 1,2. -Epoxy-5-hexene, 1,7-octadiene monoepoxiside and the like can be mentioned.

Examples of the styrene compound include styrene having no hydroxy group, for example, styrene, α-methylstyrene, chlorostyrene, bromostyrene and the like.

In the production of the alkali-soluble acrylic polymer as the component (B), the ratio of the other monomers is preferably 80% by weight or less, more preferably 50% by weight or less, still more preferably 20% by weight or less. .. If it is more than 80% by weight, the essential components are relatively reduced, so that it becomes difficult to sufficiently obtain the effects of the present invention.

The method for obtaining the alkali-soluble acrylic polymer which is the component (B) used in the present invention is not particularly limited, and for example, a carboxyl group, a phenolic hydroxy group, and a carboxylic acid or a phenolic hydroxy group by the action of heat or acid can be obtained. Monomer having at least one selected from the group consisting of the groups to be produced, monomer having an aliphatic hydroxyl group, N-substituted maleimide, monomer having an epoxy group), optionally other copolymerizable monomers, and optionally initiating polymerization. It is obtained by carrying out a polymerization reaction at a temperature of 50 to 110 ° C. in a solvent in which an agent or the like coexists. At that time, the solvent used is not particularly limited as long as it dissolves the monomer constituting the alkali-soluble acrylic polymer and the acrylic polymer having a specific functional group. Specific examples include the solvent described in (D) Solvent described later.

The acrylic polymer having a specific functional group thus obtained is usually in the state of a solution dissolved in a solvent.

Further, the solution of the specific copolymer obtained as described above is added under stirring with diethyl ether, water or the like to reprecipitate, and the generated precipitate is filtered and washed, and then under normal pressure or reduced pressure. Then, the powder of the specific copolymer can be obtained by drying at room temperature or by heating. By such an operation, the polymerization initiator and the unreacted monomer coexisting with the specific copolymer can be removed, and as a result, the purified powder of the specific copolymer can be obtained. If the powder cannot be sufficiently purified by one operation, the obtained powder may be redissolved in a solvent and the above operation may be repeated.
In the present invention, the powder of the specific copolymer may be used as it is, or the powder may be redissolved in, for example, the solvent (D) described later and used as a solution.

Further, as the alkali-soluble resin of the component (B), a polyimide precursor such as polyamic acid, polyamic acid ester, partially imidized polyamic acid, or polyimide such as carboxylic acid group-containing polyimide can be used, and these are alkali. As long as it is soluble, the type can be used without particular limitation.

The polyamic acid, which is a polyimide precursor, can generally be obtained by polycondensing (a) a tetracarboxylic dianhydride compound and (b) a diamine compound.

The above (a) tetracarboxylic dianhydride compound is not particularly limited, and as specific examples, pyromellitic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 3,3'. , 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-diphenyl ethertetracarboxylic dianhydride, 3,3', 4,4'-diphenylsulfonetetracarboxylic dianhydride Such as aromatic tetracarboxylic acids, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2, 3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,3,4-cyclohexanetetra Alicyclic tetracarboxylic dianhydride, 1,2,3, such as carboxylic acid dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalensuccinic dianhydride, Examples thereof include aliphatic tetracarboxylic dianhydrides such as 4-butanetetracarboxylic dianhydride.
These may be used individually by 1 type, or may be used in combination of 2 or more types.

The diamine compound (b) is also not particularly limited, and for example, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, 4,6-diamino-1. , 3-Benzene dicarboxylic acid, 2,5-diamino-1,4-benzenedicarboxylic acid, bis (4-amino-3-carboxyphenyl) ether, bis (4-amino-3,5-dicarboxyphenyl) ether, Bis (4-amino-3-carboxyphenyl) sulfone, Bis (4-amino-3,5-dicarboxyphenyl) sulfone, 4,4'-diamino-3,3'-dicarboxybiphenyl, 4,4'- Diamino-3,3'-dicarboxy-5,5'-dimethylbiphenyl, 4,4'-diamino-3,3'-dicarboxy-5,5'-dimethoxybiphenyl, 1,4-bis (4-amino) -3-carboxyphenoxy) benzene, 1,3-bis (4-amino-3-carboxyphenoxy) benzene, bis [4- (4-amino-3-carboxyphenoxy) phenyl] sulfone, bis [4- (4- (4- (4- (4-) 4-) Amino-3-carboxyphenoxy) phenyl] propane, 2,2-bis [4- (4-amino-3-carboxyphenoxy) phenyl] hexafluoropropane, 2,4-diaminophenol, 3,5-diaminophenol, 2 , 5-Diaminophenol, 4,6-diaminoresorcinol, 2,5-diaminohydroquinone, bis (3-amino-4-hydroxyphenyl) ether, bis (4-amino-3-hydroxyphenyl) ether, bis (4-) Amino-3,5-dihydroxyphenyl) ether, bis (3-amino-4-hydroxyphenyl) methane, bis (4-amino-3-hydroxyphenyl) methane, bis (4-amino-3,5-dihydroxyphenyl) Methan, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, bis (4-amino-3,5-dihydroxyphenyl) sulfone, 2,2-bis (3) -Amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis (4-amino-3-hydroxyphenyl) hexafluoropropane, 2,2-bis (4-amino-3,5-dihydroxyphenyl) hexafluoro Propane, 4,4'-diamino-3,3'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxy-5,5'-dimethylbiphenyl Le, 4,4'-diamino-3,3'-dihydroxy-5,5'-dimethoxybiphenyl, 1,4-bis (3-amino-4-hydroxyphenoxy) benzene, 1,3-bis (3-amino) -4-Hydroxyphenoxy benzene, 1,4-bis (4-amino-3-hydroxyphenoxy) benzene, 1,3-bis (4-amino-3-hydroxyphenoxy) benzene, bis [4- (3-amino) -4-Hydroxyphenoxy) phenyl] sulfonate, bis [4- (3-amino-4-hydroxyphenoxy) phenyl] propane, 2,2-bis [4- (3-amino-4-hydroxyphenoxy) phenyl] hexafluoro Diamine compounds having a phenolic hydroxy group such as propane, 1,3-diamino-4-mercaptobenzene, 1,3-diamino-5-mercaptobenzene, 1,4-diamino-2-mercaptobenzene, bis (4-amino-) Diamine compounds having a thiophenol group such as 3-mercaptophenyl) ether, 2,2-bis (3-amino-4-mercaptophenyl) hexafluoropropane, 1,3-diaminobenzene-4-sulfonic acid, 1,3- Diaminobenzene-5-sulfonic acid, 1,4-diaminobenzene-2-sulfonic acid, bis (4-aminobenzene-3-sulfonic acid) ether, 4,4'-diaminobiphenyl-3,3'-disulfonic acid, Examples thereof include diamine compounds having a sulfonic acid group such as 4,4'-diamino-3,3'-dimethylbiphenyl-6,6'-disulfonic acid. In addition, p-phenylenediamine, m-phenylenediamine, 4,4'-methylene-bis (2,6-ethylaniline), 4,4'-methylene-bis (2-isopropyl-6-methylaniline), 4, 4'-Methylene-bis (2,6-diisopropylaniline), 2,4,6-trimethyl-1,3-phenylenediamine, 2,3,5,6-tetramethyl-1,4-phenylenediamine, o- Trizine, m-trizine, 3,3', 5,5'-tetramethylbenzidine, bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (3-aminophenoxy) phenyl] Propane, 2,2-bis [4- (3-aminophenoxy) phenyl] hexafluoropropane, 4,4'-diamino-3,3'-dimethyldicyclohexylmethane, 4,4'-diaminodiphenyl ether, 3,4- Diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 2,2-bis (4-anilino) hexafluoropropane, 2,2-bis (3-anilino) hexafluoropropane, 2,2-bis (3-amino-4) -Truyl) hexafluoropropane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, bis [4- (4-aminophenoxy) phenyl] sulfone, 2,2 Diamines such as −bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2′-bis (trifluoromethyl) benzidine Compounds can be mentioned.
These may be used individually by 1 type, or may be used in combination of 2 or more types.

When the polyamic acid used in the present invention is produced from (a) a tetracarboxylic dianhydride compound and (b) a diamine compound, the compounding ratio of both compounds, that is, (b) the total number of moles of the diamine compound / (a). The total number of moles of the tetracarboxylic dianhydride compound is preferably 0.7 to 1.2. Similar to a normal polycondensation reaction, the closer the molar ratio is to 1, the greater the degree of polymerization of the polyamic acid produced and the higher the molecular weight.

Further, when the diamine compound is excessively used for polymerization, the carboxylic acid anhydride can be reacted with the terminal amino group of the remaining polyamic acid to protect the terminal amino group.
Examples of such carboxylic acid anhydrides are phthalic anhydride, trimellitic anhydride, maleic anhydride, naphthalic anhydride, hydride phthalic anhydride, methyl-5-norbornene-2,3-dicarboxylic acid. Anhydride, itaconic anhydride, tetrahydrophthalic anhydride and the like can be mentioned.

In the production of the polyamic acid, the reaction temperature of the reaction between the diamine compound and the tetracarboxylic dianhydride compound can be selected from −20 to 150 ° C., preferably −5 to 100 ° C. In order to obtain a high molecular weight polyamic acid, a reaction temperature of 5 ° C. to 40 ° C. and a reaction time of 1 to 48 hours are appropriately selected. In order to obtain a partially imidized polyamic acid having a low molecular weight and high storage stability, it is more preferable to select from a reaction temperature of 40 ° C. to 90 ° C. and a reaction time of 10 hours or more.
Further, when the terminal amino group is protected with an acid anhydride, the reaction temperature can be selected from −20 to 150 ° C., preferably −5 to 100 ° C.

The reaction of the diamine compound and the tetracarboxylic dianhydride compound can be carried out in a solvent. Solvents that can be used at this time include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, N-vinylpyrrolidone, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, etc. Hexamethyl sulfoxide, m-cresol, γ-butyrolactone, ethyl acetate, butyl acetate, ethyl lactate, methyl 3-methoxypropionate, methyl 2-methoxypropionate, ethyl 3-methoxypropionate, ethyl 2-methoxypropionate, 3 -Ethyl ethoxypropionate, ethyl 2-ethoxypropionate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol Monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, carbitol acetate, ethyl cellosolve acetate, cyclohexanone, methyl ethyl ketone, Examples thereof include methyl isobutyl ketone and 2-heptanone. These may be used alone or in combination. Further, even if the solvent does not dissolve the polyamic acid, it may be mixed with the above solvent and used as long as the polyamic acid produced by the polymerization reaction does not precipitate.

The solution containing the polyamic acid thus obtained can be used as it is for the preparation of the negative photosensitive resin composition. Further, the polyamic acid can be recovered and used by precipitating and isolating it in a poor solvent such as water, methanol or ethanol.

Further, as the component (B), any polyimide can be used. The polyimide used in the present invention is a polyimide precursor such as the polyamic acid chemically or thermally imidized by 50% or more.

The polyimide used in the positive photosensitive resin composition of the present invention preferably has a group selected from a carboxyl group and a phenolic hydroxy group in order to impart alkali solubility.
The method for introducing a carboxyl group or a phenolic hydroxy group into the polyimide is a method using a monomer having a carboxyl group or a phenolic hydroxy group, a method of sealing the amine terminal with an acid anhydride having a carboxyl group or a phenolic hydroxy group, and a method. Alternatively, a method of reducing the imidization rate to 99% or less when imidizing a polyimide precursor such as polyamic acid is used.

Such a polyimide can be obtained by synthesizing a polyimide precursor such as the above-mentioned polyamic acid and then performing chemical imidization or thermal imidization.
As a method of chemical imidization, a method of adding excess acetic anhydride and pyridine to a polyimide precursor solution and reacting at room temperature to 100 ° C. is generally used. Further, as a method of thermal imidization, a method of heating a polyimide precursor solution while dehydrating it at a temperature of 180 ° C. to 250 ° C. is generally used.

Further, as the alkali-soluble resin of the component (B), a phenol novolac resin can be further used.

Further, as the alkali-soluble resin of the component (B), a polyester polycarboxylic acid can also be used. Polyester polycarboxylic acid can be obtained from acid dianhydride and diol by the method described in WO2009 / 051186.
Examples of the acid dianhydride include the above-mentioned (a) tetracarboxylic dianhydride.
Examples of the diol include aromatic diols such as bisphenol A, bisphenol F, 4,4'-dihydroxybiphenyl, benzene-1,3-dimethanol, benzene-1,4-dimethanol, hydrogenated bisphenol A, and hydrogenated bisphenol F. , 1,4-Cyclohexanediol, 1,3-Cyclohexanedimethanol, alicyclic diols such as 1,4-cyclohexanedimethanol, and ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol. And the like, aliphatic diols and the like.

Further, in the present invention, the alkali-soluble resin of the component (B) may be a mixture of a plurality of types of alkali-soluble resins.

The ratio of the component (A) to the component (B) is 0.1 to 20 parts by mass for the component (A) with respect to 100 parts by mass for the component (B).

<Component (C)>
The 1,2-quinonediazide compound as the component (C) is a compound having either a hydroxyl group or an amino group, or both a hydroxyl group and an amino group, and these hydroxyl groups or amino groups (of the hydroxyl group and the amino group). If both are present, preferably 10 to 100 mol%, particularly preferably 20 to 95 mol% of the total amount thereof) is esterified or amidated with 1,2-quinonediazide sulfonic acid. be able to.

Examples of the compound having a hydroxyl group include phenol, o-cresol, m-cresol, p-cresol, hydroquinone, resorcinol, catechol, methyl gallicate, ethyl gallicate, 1,3,3-tris (4-hydroxyphenyl). Butane, 4,4-isopropridenediphenol, 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4'-dihydroxyphenylsulfone, 4,4- Hexafluoroisopropyridene diphenol, 4,4', 4''-trishydroxyphenylethane, 1,1,1-trishydroxyphenylethane, 4,4'-[1- [4- [1- (4-hydroxy) Phenyl) -1-methylethyl] phenyl] ethylidene] bisphenol, 2,4-dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,2', 4,4'-tetrahydroxybenzophenone, 2,3,4 , 4'-Tetrahydroxybenzophenone, 2,2', 3,4,4'-pentahydroxybenzophenone, phenolic compounds such as 2,5-bis (2-hydroxy-5-methylbenzyl) methyl, ethanol, 2-propanol , 4-Butanol, Cyclohexanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 2-methoxyethanol, 2-butoxyethanol, 2-methoxypropanol, 2-butoxypropanol, ethyl lactate, butyl lactate and other aliphatic alcohols. Can be mentioned.

Examples of the amino group-containing compound include aniline, o-toluidine, m-toluidine, p-toluidine, 4-aminodiphenylmethane, 4-aminodiphenyl, o-phenylenediamine, m-phenylenediamine, and p-phenylenediamine. , 4,4'-Diaminophenylmethane, 4,4'-diaminodiphenyl ether, and other anilines, aminocyclohexane can be mentioned.

Further, examples of the compound containing both a hydroxyl group and an amino group include o-aminophenol, m-aminophenol, p-aminophenol, 4-aminoresorcinol, 2,3-diaminophenol, and 2,4-diaminophenol. 4,4'-Diamino-4''-hydroxytriphenylmethane, 4-amino-4', 4''-dihydroxytriphenylmethane, bis (4-amino-3-carboxy-5-hydroxyphenyl) ether, bis (4-Amino-3-carboxy-5-hydroxyphenyl) methane, 2,2-bis (4-amino-3-carboxy-5-hydroxyphenyl) propane, 2,2-bis (4-amino-3-carboxy) Examples thereof include aminophenols such as −5-hydroxyphenyl) hexafluoropropane, and alkanolamines such as 2-aminoethanol, 3-aminopropanol, and 4-aminocyclohexanol.

These 1,2-quinonediazide compounds can be used alone or in combination of two or more.

The content of the component (C) in the positive photosensitive resin composition of the present invention is preferably 5 to 100 parts by mass, more preferably 8 with respect to 100 parts by mass of the total of the components (A) and (B). It is to 50 parts by mass, more preferably 10 to 40 parts by mass. If it is less than 5 parts by mass, the difference in dissolution rate between the exposed portion and the unexposed portion of the positive photosensitive resin composition in the developing solution becomes small, and patterning by development may be difficult. On the other hand, if it exceeds 100 parts by mass, the 1,2-quinonediazide compound is not sufficiently decomposed by exposure in a short time, so that the sensitivity is lowered, or the component (C) absorbs light and the transparency of the cured film is transparent. May be reduced.

<(D) Solvent>
The solvent (D) used in the present invention dissolves the component (A), the component (B), the component (C), and the component (E) if necessary, and is added as desired. And other additives are dissolved, and the type and structure of the solvent are not particularly limited as long as it is a solvent having such a dissolving ability.

Examples of such (D) solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, and propylene glycol. Monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-butanone, 3-methyl-2-pentanone, 2-pentanone, 2-heptanone, γ-butyrolactone, 2-hydroxypropion Ethyl acetate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropion Ethyl acetate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, etc. Can be mentioned.

These solvents can be used alone or in combination of two or more.
Among these (D) solvents, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 2-heptanone, propylene glycol propyl ether, propylene glycol propyl ether acetate, ethyl lactate, butyl lactate and the like have good coating properties and are safe. Is preferable from the viewpoint of high. These solvents are generally used as solvents for photoresist materials.

<Ingredient (E)>
The component (E) is a cross-linking agent, which is introduced into the composition when the positive photosensitive resin composition of the present invention satisfies the requirement (Z1). More specifically, it is a compound having a structure capable of forming a bridging structure by a thermal reaction with a thermally reactive site (for example, a carboxyl group and / or a phenolic hydroxyl group) of the component (B). Specific examples will be given below, but the present invention is not limited to these. The heat cross-linking agent is selected from, for example, a cross-linking compound having two or more substituents selected from (E1) alkoxymethyl group and hydroxymethyl group, and a cross-linking compound represented by the formula (2) (2). preferable. These cross-linking agents can be used alone or in combination of two or more.

When the crosslinkable compound having two or more substituents selected from the alkoxymethyl group and the hydroxymethyl group of the component (E1) is exposed to a high temperature during heat curing, the crosslinking reaction proceeds by the dehydration condensation reaction. .. Examples of such compounds include compounds such as alkoxymethylated glycol uryl, alkoxymethylated benzoguanamine, and alkoxymethylated melamine, and phenoplast compounds.

Specific examples of alkoxymethylated glycol uryl include 1,3,4,6-tetrax (methoxymethyl) glycol uryl, 1,3,4,6-tetrakis (butoxymethyl) glycol uryl, 1,3,4. , 6-Tetrax (hydroxymethyl) glycoluryl, 1,3-bis (hydroxymethyl) urea, 1,1,3,3-tetrakis (butoxymethyl) urea, 1,1,3,3-tetrakis (methoxymethyl) Examples include urea, 1,3-bis (hydroxymethyl) -4,5-dihydroxy-2-imidazolinone, and 1,3-bis (methoxymethyl) -4,5-dimethoxy-2-imidazolinone. As commercially available products, compounds such as glycoluril compounds manufactured by Mitsui Cytec Co., Ltd. (trade name: Cymel (registered trademark) 1170, powder link (registered trademark) 1174), methylated urea resin (trade name: UFR (registered trademark) 65) ), Butylated urea resin (trade name: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), urea / formaldehyde resin manufactured by DIC Co., Ltd. (high condensation type, trade name: Beccamin () Registered trademarks) J-300S, P-955, N) and the like.

Specific examples of the alkoxymethylated benzoguanamine include tetramethoxymethylbenzoguanamine. As commercial products, Mitsui Cytec Co., Ltd. (trade name: Cymel (registered trademark) 1123), Sanwa Chemical Co., Ltd. (trade name: Nicarac (registered trademark) BX-4000, BX-37, BL- 60, BX-55H) and the like.

Specific examples of the alkoxymethylated melamine include hexamethoxymethylmelamine and the like. Commercially available products include methoxymethyl type melamine compounds manufactured by Mitsui Cytec Co., Ltd. (trade name: Cymel (registered trademark) 300, 301, 303, 350), butoxymethyl type melamine compound (trade name: Mycoat (registered trademark)). ) 506, 508), Sanwa Chemical's methoxymethyl type melamine compound (trade name: Nicarac (registered trademark) MW-30, MW-22, MW-11, MW-100LM, MS-001, MS-001, same MX-002, MX-730, MX-750, MX-035), butoxymethyl type melamine compounds (trade name: Nicarac (registered trademark) MX-45, MX-410, MX-302), etc. Can be mentioned.

Further, it may be a compound obtained by condensing such a melamine compound, a urea compound, a glycoluril compound and a benzoguanamine compound in which the hydrogen atom of the amino group is substituted with a methylol group or an alkoxymethyl group. For example, high molecular weight compounds produced from the melamine and benzoguanamine compounds described in US Pat. No. 6,323,310. Examples of commercially available products of the melamine compound include trade name: Cymel (registered trademark) 303 (manufactured by Mitsui Cytec Co., Ltd.), and commercial products of the benzoguanamine compound include trade name: Cymel (registered trademark) 1123 ( Mitsui Cytec Co., Ltd.) and the like.

Specific examples of the phenoplast compound include 2,6-bis (hydroxymethyl) phenol, 2,6-bis (hydroxymethyl) cresol, 2,6-bis (hydroxymethyl) -4-methoxyphenol, and 3 , 3', 5,5'-tetrax (hydroxymethyl) biphenyl-4,4'-diol, 3,3'-methylenebis (2-hydroxy-5-methylbenzenemethanol), 4,4'-(1-methyl) Ethiliden) bis [2-methyl-6-hydroxymethylphenol], 4,4'-methylenebis [2-methyl-6-hydroxymethylphenol], 4,4'-(1-methylethylidene) bis [2,6-- Bis (hydroxymethyl) phenol], 4,4'-methylenebis [2,6-bis (hydroxymethyl) phenol], 2,6-bis (methoxymethyl) phenol, 2,6-bis (methoxymethyl) cresol, 2 , 6-bis (methoxymethyl) -4-methoxyphenol, 3,3', 5,5'-tetrakis (methoxymethyl) biphenyl-4,4'-diol, 3,3'-methylenebis (2-methoxy-5) -Methylbenzene methanol), 4,4'-(1-methylethylidene) bis [2-methyl-6-methoxymethylphenol], 4,4'-methylenebis [2-methyl-6-methoxymethylphenol], 4, Examples thereof include 4'-(1-methylethylidene) bis [2,6-bis (methoxymethyl) phenol], 4,4'-methylenebis [2,6-bis (methoxymethyl) phenol], and the like. It is also available as a commercially available product, and specific examples thereof include 26DMPC, 46DMOC, DM-BIPC-F, DM-BIOC-F, TM-BIP-A, BISA-F, BI25X-DF, and BI25X-TPA ( As mentioned above, Asahi Organic Materials Industry Co., Ltd.) and the like can be mentioned.

Further, as the component (E1), an acrylamide compound substituted with a hydroxymethyl group such as N-hydroxymethylacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethylacrylamide, N-butoxymethylmethacrylamide, or an alkoxymethyl group or Polymers made using methacrylamide compounds can also be used.

Examples of such a polymer include poly (N-butoxymethylacrylamide), a copolymer of N-butoxymethylacrylamide and styrene, a copolymer of N-hydroxymethylmethacrylamide and methylmethacrylate, and N-ethoxymethyl. Examples thereof include a copolymer of methacrylamide and benzyl methacrylate, and a copolymer of N-butoxymethyl acrylamide, benzyl methacrylate and 2-hydroxypropyl methacrylate. The weight average molecular weight of such a polymer is 1,000 to 50,000, preferably 1,500 to 20,000, and more preferably 2,000 to 10,000.

Further, the positive photosensitive resin composition of the present invention can contain a crosslinkable compound represented by the formula (2) as a component (E2).
(In the formula, k represents an integer of 2 to 10, m represents an integer of 0 to 4, and R ¹¹ represents a k-valent organic group.)

The component (E2) is not particularly limited as long as it is a compound having a cycloalkene oxide structure represented by the formula (2). Specific examples thereof include the following formulas E2-1 and E2-2, and commercially available products shown below.

Commercially available products include Epolide GT-401, GT-403, GT-301, GT-302, Selokiside 2021, Selokiside 3000 (trade name manufactured by Dicel Chemical Industries, Ltd.), and Denacol, which is an alicyclic epoxy resin. EX-252 (trade name made by Nagase Chemutex Co., Ltd.), CY175, CY177, CY179 (above, product name made by CIBA-GEIGY AG), Araldite CY-182, CY-192, CY-184 ( Above, CIBA-GEIGY AG product name), Epicron 200, 400 (Product name by DIC Corporation), Epicoat 871, 872 (Product name by Yuka Shell Epoxy Co., Ltd.), Examples thereof include ED-5661 and ED-5662 (hereinafter, trade names manufactured by Ceranies Coating Co., Ltd.). In addition, these crosslinkable compounds can be used alone or in combination of two or more.

Among these, compounds represented by formulas C1 and C2 having a cyclohexene oxide structure from the viewpoint of process resistance such as heat resistance, solvent resistance, long-term firing resistance, and transparency, Epolide GT-401, The GT-403, the GT-301, the GT-302, the sinterside 2021, and the seroxside 3000 are preferable.

When the component (B) has a group that reacts with at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, and a group represented by an amino group, the hydroxy group, the carboxyl group, the amide group, and the like. A compound having two or more groups represented by amino groups can be used as the component (E).

These crosslinkable compounds can be used alone or in combination of two or more.

When the component (E) is selected as the cross-linking agent in the positive photosensitive resin composition of the present invention, the content is 1 to 50 parts by mass with respect to 100 parts by mass in total of the components (A) and (B). It is preferably 1 to 40 parts by mass, and more preferably 1 to 30 parts by mass. When the content of the crosslinkable compound is small, the density of the crosslinks formed by the crosslinkable compound is not sufficient, so that the effect of improving the heat resistance, solvent resistance, resistance to long-term firing, etc. after pattern formation is improved. May not be obtained. On the other hand, when it exceeds 50 parts by mass, an uncrosslinked crosslinkable compound is present, and the heat resistance, solvent resistance, resistance to long-term firing, etc. after pattern formation are lowered, and the photosensitive resin composition Storage stability may deteriorate.

<(F) component>
The component (F) is an antifoaming agent. The positive photosensitive resin composition of the present invention may further contain an antifoaming agent for the purpose of improving the coatability thereof, as long as the effects of the present invention are not impaired.

The defoaming agent for the component (F) is not particularly limited, and examples thereof include silicone and the like.
The defoaming agent of the component (F) can be used alone or in combination of two or more.

When an antifoaming agent is used, its content is usually 0.01 to 1.0 parts by mass, preferably 0.02, based on 100 parts by mass of the total of the components (A) and (B). To 0.8 parts by mass. Even if the amount of the defoaming agent used as the component (F) is set to exceed 1.0 part by mass, the effect of improving the coatability becomes dull and uneconomical. If it is 0.01 part or less, the effect of improving the coatability may not be exhibited.

<Other additives>
Further, the positive photosensitive resin composition of the present invention may be a rheology adjuster, a pigment, a dye, a storage stabilizer, a defoaming agent, an adhesion accelerator, or, if necessary, as long as the effect of the present invention is not impaired. It can contain a dissolution accelerator such as polyhydric phenol and polyvalent carboxylic acid.

<Positive photosensitive resin composition>
The positive photosensitive resin composition of the present invention is a positive photosensitive resin composition containing the following components (A), (B), (C) and (D) solvent, and if desired, It is a composition capable of further containing one or more of the adhesion promoter of the component (F) and other additives.
Component (A): Polymer having a liquid-repellent group and a quinonediazide group,
(B) Ingredient: Alkali-soluble resin;
(C) Ingredient: 1,2-quinonediazide compound,
(D) Solvent.

The photosensitive resin composition of the present invention preferably further satisfies at least one of the following (Z1) and (Z2).
(Z1): Further contains a cross-linking agent which is a component (E).
(Z2): A group in which the alkali-soluble resin of the component (B) further has a self-crosslinkable group or reacts with at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group and an amino group. Have more.

Among them, preferable examples of the positive photosensitive resin composition of the present invention are as follows.
[1]: Contains 0.1 to 20 parts by mass of the component (A) with respect to 100 parts by mass of the component (B), and 5 to 100 parts by mass of the component (C), and these components are dissolved in the solvent (D). A positive photosensitive resin composition obtained by the above, wherein the alkali-soluble resin of the component (B) further has a repeating unit having an epoxy group.
[2]: Contains 0.1 to 20 parts by mass of component (A) and 5 to 100 parts by mass of component (C) with respect to 100 parts by mass of component (B), and these components are dissolved in the solvent (D). The positive-type photosensitive resin composition, which further contains 1 to 50 parts by mass of a cross-linking agent which is a component (E) with respect to 100 parts by mass of the total of the components (A) and (B). Mold photosensitive resin composition.
[3]: In the composition of the above [1] or [2], a positive photosensitive resin further containing 0.01 to 1.0 parts by mass of component (F) based on 100 parts by mass of component (A). Composition.

The proportion of the solid content in the positive photosensitive resin composition of the present invention is not particularly limited as long as each component is uniformly dissolved in the solvent, but is, for example, 1 to 80% by mass, and for example. It is 5 to 60% by mass, or 10 to 50% by mass. Here, the solid content refers to the one obtained by removing the solvent (D) from all the components of the positive photosensitive resin composition.

The method for preparing the positive photosensitive resin composition of the present invention is not particularly limited, but as the method for preparing the positive photosensitive resin composition, for example, the component (A) (specific acrylic copolymer) is dissolved in the solvent (D), and this solution is used. A method of mixing the alkali-soluble resin of the component (B), the 1,2-quinonediazide compound of the component (C), and the cross-linking agent of the component (E) in a predetermined ratio as required to obtain a uniform solution, or At an appropriate stage of this preparation method, a method of further adding and mixing the antifoaming agent and other additives as the component (F) can be mentioned as needed.

In the preparation of the positive photosensitive resin composition of the present invention, the solution of the copolymer obtained by the polymerization reaction in the solvent (D) can be used as it is, and in this case, the solution of the component (A) can be used as it is. In the same manner as described above, when the component (B), the component (C) and the like are added to form a uniform solution, the solvent (D) may be further added for the purpose of adjusting the concentration. At this time, the solvent (D) used in the process of forming the specific copolymer and the solvent (D) used for adjusting the concentration at the time of preparing the positive photosensitive resin composition may be the same. It may be different.

Therefore, it is preferable that the prepared solution of the positive photosensitive resin composition is used after being filtered using a filter having a pore size of about 0.2 μm or the like.

<Coating film and cured film>
The positive photosensitive resin composition of the present invention is applied to a semiconductor substrate (for example, a silicon / silicon dioxide coated substrate, a silicon nitride substrate, a substrate coated with a metal such as aluminum, molybdenum, chromium, etc., a glass substrate, a quartz substrate, an ITO substrate). Etc.), a coating film is formed by applying by rotary coating, sink coating, roll coating, slit coating, rotary coating following the slit, inkjet coating, etc., and then pre-drying with a hot plate or oven. can do. Then, by heat-treating this coating film, a positive photosensitive resin film is formed.

As the conditions for this heat treatment, for example, a heating temperature and a heating time appropriately selected from a temperature range of 70 ° C. to 160 ° C. and a time range of 0.3 to 60 minutes are adopted. The heating temperature and heating time are preferably 80 ° C. to 140 ° C. and 0.5 to 10 minutes.

The film thickness of the positive photosensitive resin film formed from the positive photosensitive resin composition is, for example, 0.1 to 30 μm, for example 0.2 to 10 μm, and further, for example 0.3 to 8 μm. Is.

A mask having a predetermined pattern is attached to the coating film obtained above, irradiated with light such as ultraviolet rays, and developed with an alkaline developer to wash out the exposed part and have a sharp relief pattern on the end face. Is obtained.

Examples of the alkaline developing solution that can be used include aqueous solutions of alkali metal hydroxides such as potassium carbonate, sodium carbonate, potassium hydroxide and sodium hydroxide, and hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline. Examples thereof include an aqueous solution of quaternary ammonium and an alkaline aqueous solution such as an aqueous solution of amines such as ethanolamine, propylamine and ethylenediamine. Further, a surfactant or the like can be added to these developers.

Among the above, a 0.1 to 2.38 mass% aqueous solution of tetraethylammonium hydroxide is generally used as a developing solution for a photoresist, and the photosensitive resin composition of the present invention also uses this alkaline developing solution. , Can be developed well without causing problems such as swelling.

Further, as the developing method, any of a liquid filling method, a dipping method, a rocking dipping method and the like can be used. The developing time at that time is usually 15 to 180 seconds.

After development, the positive photosensitive resin film is washed with running water for, for example, 20 to 120 seconds, followed by air drying with compressed air or compressed nitrogen or by spinning to remove moisture on the substrate. A patterned film is obtained.

Subsequently, the pattern-forming film is post-baked for thermosetting, and specifically, by heating using a hot plate, an oven, or the like, heat resistance, transparency, and flattening property are achieved. A film having a good relief pattern can be obtained, which is excellent in low water absorption and chemical resistance.

Post-baking is generally performed at a heating temperature selected from the temperature range of 140 ° C. to 270 ° C. for 5 to 30 minutes on a hot plate and 30 to 90 minutes in an oven. The method is adopted.

Thus, such a postbake makes it possible to obtain a desired cured film having a good pattern shape.

As described above, the positive photosensitive resin composition of the present invention has high storage stability, sufficiently high sensitivity, very small film loss in the unexposed portion during development, and a coating having a fine pattern. A film can be formed.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. The measurement of the number average molecular weight and the weight average molecular weight is as follows.
[Measurement of number average molecular weight and weight average molecular weight]
The number average molecular weight and weight average molecular weight of the copolymers obtained according to the following synthesis examples were determined by using a GPC apparatus (Shodex column KD800 and TOSOH column TSK-GEL) manufactured by Toso Co., Ltd. and elution solvents N, N'-dimethyl. A condition that formamide (mixed with 10 mmol / L (liter) of lithium bromide-hydrate (LiBr · H ₂ O) as an additive) is allowed to flow through the column (column temperature 40 ° C.) at a flow rate of 1 ml / min to elute. Measured at. The following number average molecular weight (hereinafter referred to as Mn) and weight average molecular weight (hereinafter referred to as Mw) are represented by polystyrene-equivalent values.

The meanings of the abbreviations used in the following examples are as follows.
MMA: Methyl methacrylate HEMA: 2-Hydroxyethyl methacrylate HPMA: 4-Hydroxyphenyl methacrylate HPMA-QD: Condensation reaction of 1 mol of 4-hydroxyphenyl methacrylate with 1.1 mol of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride Compounds synthesized by CHMI: N-cyclohexylmaleimideTMSSMA: Methacryloxypropyltris (trimethylsiloxy) Silane PFHMA: 2- (Perfluorohexyl) Ethylmethacrylate MAA: BEMAmethacrylate: 1-Butoxyethylmethacrylate TBMA: t-butylmethacrylate GMA: Glycidyl Methacrylate AIBN: α, α'-Azobisisobutyronitrile BHT: Dibutylhydroxytoluene QDC: 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride TEA: Triethylamine QD1: 4,4', 4 " -(3-Methyl-1-propanol-3-ylidene) A compound synthesized by a condensation reaction of 1 mol of trisphenol with 1.5 mol of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride QD2: α, α, Compound CEL-2021P synthesized by a condensation reaction of 1 mol of α'-tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene and 1.5 mol of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride. : 3,4-Epoxycyclohexylmethyl-3', 4'-epoxycyclohexanecarboxylate GT-401: Tetra butanetetracarboxylic acid (3,4-epoxycyclohexylmethyl) modified ε-caprolactone SH-7: Toray Dowcorning ( PGME: Propyl glycol monomethyl ether PGMEA: Propyl glycol monomethyl ether acetate CHN: Cyclohexanone

<Synthesis example 1>
7.50 g (42.1 mmol) of HPMA, 12.44 g (46.3 mmol) of QDC, and 225.4 g of toluene were charged in a 500 mL four-necked flask, and 5.11 g (50.5 mmol) of TEA was added dropwise under stirring. The mixture was stirred at 20 to 25 ° C. for 20 hours. Subsequently, after removing TEA hydrochloride with water, the precipitated crystals were filtered, washed with toluene, and dried under reduced pressure to obtain 12.3 g (yield 71.4%) of HPMA-QD light orange crystals.

<Synthesis example 2>
Acrylic polymer solution by dissolving 7.20 g of MMA, 7.20 g of HEMA, 10.8 g of CHMI, 4.32 g of MAA and 2.46 g of AIBN in 46.9 g of PGMEA and reacting at 60 ° C to 100 ° C for 20 hours. (Solid content concentration 40% by mass) was obtained (P1). The obtained acrylic polymer had Mn of 3,800 and Mw of 7,300.

<Synthesis example 3>
MMA 10.0 g, HEMA 12.5 g, CHMI 20.0 g, HPMA 2.50 g, MAA 5.00 g, AIBN 3.20 g are dissolved in PGME 79.8 g and reacted at 60 ° C to 100 ° C for 20 hours. Acrylic polymer solution (solid content concentration 40% by mass) was obtained (P2). The obtained acrylic polymer had Mn of 3,700 and Mw of 6,100.

<Synthesis example 4>
TBMA 0.80 g, TMSSMA 3.20 g, PFHMA 6.24 g, HEMA 1.76 g, MAA 1.60 g, CHMI 1.60 g, BEMA 0.80 g, AIBN 0.56 g were dissolved in PGMEA 38.7 g and heated to 90 ° C. Acrylic polymer solution (solid content concentration: 30% by mass) was obtained by stirring for 20 hours (P3). The obtained acrylic polymer had Mn of 6,300 and Mw of 10,000.

<Synthesis example 5>
Acrylic weight by dissolving 1.00 g of HPMA, 2.38 g of TMSSMA, 4.85 g of PFHMA, 0.64 g of MAA, 1.34 g of CHMI and 0.31 g of AIBN in 24.5 g of PGMEA and stirring at 110 ° C. for 20 hours. A coalesced solution (solid content concentration 30% by mass) was obtained (P4). The obtained acrylic polymer had Mn of 6,400 and Mw of 10,600.

<Synthesis example 6>
By dissolving 2.50 g of HPMA-QD, 2.58 g of TMSSMA, 5.26 g of PFHMA, 0.70 g of MAA, 1.46 g of CHMI and 0.33 g of AIBN in 51.3 g of CHN and stirring at 110 ° C. for 20 hours. An acrylic polymer solution (solid content concentration 20% by mass) was obtained (P5). The obtained acrylic polymer had Mn of 7,200 and Mw of 11,000.

<Synthesis example 7>
Acrylic polymer solution P4 10.0 g, QDC 0.48 g, and TEA 0.20 g were stirred at room temperature for 20 hours. Subsequently, TEA hydrochloride was filtered off and reprecipitated with hexane to obtain an acrylic polymer (P6). The obtained acrylic polymer had Mn of 10,200 and Mw of 13,700.

<Synthesis Example 8>
Acrylic polymer solution (solid content concentration: 30% by mass) was obtained by dissolving 5.73 g of GMA, 7.00 g of HPMA, and 0.64 g of AIBN in 31.2 g of PGME and stirring at 80 ° C. for 20 hours (P7). ). The obtained acrylic polymer had Mn of 6,900 and Mw of 23,000.

<Synthesis example 9>
Acrylic polymer solution (HPMA-QD 2.50 g, PFHMA 7.84 g, MAA 0.70 g, CHMI 1.46 g, AIBN 0.33 g was dissolved in CHN 51.3 g and stirred at 110 ° C. for 20 hours. Solid content concentration 20% by mass) was obtained (P8). The obtained acrylic polymer had Mn of 4,300 and Mw of 6,300.

<Synthesis Example 10>
Acrylic polymer solution (HPMA-QD 2.50 g, TMSSMA 7.84 g, MAA 0.70 g, CHMI 1.46 g, AIBN 0.33 g was dissolved in CHN 51.3 g and stirred at 110 ° C. for 20 hours. Solid content concentration 20% by mass) was obtained (P9). The obtained acrylic polymer had Mn of 6,900 and Mw of 12,800.

<Synthesis Example 11>
By dissolving 2.50 g of HPMA-QD, 2.60 g of TMSSMA, 5.25 g of PFHMA, 0.82 g of MMA, 1.48 g of CHMI and 0.34 g of AIBN in 51.9 g of CHN and stirring at 110 ° C. for 20 hours. An acrylic polymer solution (solid content concentration 20% by mass) was obtained (P10). The obtained acrylic polymer had Mn of 9,200 and Mw of 24,200.

<Examples 1 to 7 and Comparative Examples 1 to 2>
According to the composition shown in Table 1 below, the component (A), the solution of the component (B), the component (C), the component (E), and the component (F) are dissolved in the solvent (D) at a predetermined ratio and at room temperature. The positive photosensitive resin compositions of each Example and each Comparative Example were prepared by stirring for 3 hours to obtain a uniform solution.

[Evaluation of contact angle]
Examples 1-2, Comparative Examples 1-2
A positive photosensitive resin composition was applied onto a silicon wafer using a spin coater, and then prebaked on a hot plate at a temperature of 100 ° C. for 120 seconds to form a coating film having a film thickness of 1.2 μm. This coating film was immersed in a 0.4% by mass tetramethylammonium hydroxide (hereinafter referred to as TMAH) aqueous solution for 60 seconds, and then washed with ultrapure water for 30 seconds. Next, this coating film was post-baked by heating at a temperature of 230 ° C. for 30 minutes to form a cured film having a film thickness of 1.0 μm. The contact angle of anisole on this cured film was measured using a Drop Master manufactured by Kyowa Interface Science Co., Ltd. The results obtained are shown in Table 2.

Example 3, Examples 5-7
After the positive photosensitive resin composition was applied onto a silicon wafer using a spin coater, it was prebaked on a hot plate at a temperature of 100 ° C. for 120 seconds to form a coating film having a film thickness of 1.7 μm. This coating film was immersed in a 2.38 mass% TMAH aqueous solution for 20 seconds, and then washed with ultrapure water for 20 seconds. Next, this coating film was post-baked by heating at a temperature of 230 ° C. for 30 minutes to form a cured film having a film thickness of 1.5 μm. The contact angle of anisole on this cured film was measured using a Drop Master manufactured by Kyowa Interface Science Co., Ltd. The results obtained are shown in Table 2.

Example 4
A positive photosensitive resin composition was applied onto a silicon wafer using a spin coater, and then prebaked on a hot plate at a temperature of 100 ° C. for 120 seconds to form a coating film having a film thickness of 1.2 μm. This coating film was immersed in a 1.0 mass% TMAH aqueous solution for 120 seconds, and then washed with ultrapure water for 20 seconds. Next, this coating film was post-baked by heating at a temperature of 230 ° C. for 30 minutes to form a cured film having a film thickness of 1.0 μm. The contact angle of anisole on this cured film was measured using a Drop Master manufactured by Kyowa Interface Science Co., Ltd. The results obtained are shown in Table 2.

[Evaluation of UV ozone treatment resistance]
Examples 1-2, Comparative Examples 1-2
A positive photosensitive resin composition was applied onto a silicon wafer using a spin coater, and then prebaked on a hot plate at a temperature of 100 ° C. for 120 seconds to form a coating film having a film thickness of 1.2 μm. This coating film was immersed in a 0.4% by mass TMAH aqueous solution for 60 seconds, and then washed with ultrapure water for 30 seconds. Next, this coating film was post-baked by heating at a temperature of 230 ° C. for 30 minutes to form a cured film having a film thickness of 1.0 μm. This cured film was ozone-washed for 10 minutes using UV-312 manufactured by Technovision Co., Ltd. The contact angle of the anisole on the ozone-cleaned membrane was measured using a Drop Master manufactured by Kyowa Interface Science Co., Ltd. The results obtained are shown in Table 2.

Example 3, Examples 5-7
After the positive photosensitive resin composition was applied onto a silicon wafer using a spin coater, it was prebaked on a hot plate at a temperature of 100 ° C. for 120 seconds to form a coating film having a film thickness of 1.7 μm. This coating film was immersed in a 2.38 mass% TMAH aqueous solution for 20 seconds, and then washed with ultrapure water for 20 seconds. Next, this coating film was post-baked by heating at a temperature of 230 ° C. for 30 minutes to form a cured film having a film thickness of 1.5 μm. This cured film was ozone-washed for 10 minutes using UV-312 manufactured by Technovision Co., Ltd. The contact angle of the anisole on the ozone-cleaned membrane was measured using a Drop Master manufactured by Kyowa Interface Science Co., Ltd. The results obtained are shown in Table 2.

[Evaluation of pattern shape and opening residue]
Examples 1-2, Comparative Examples 1-2
The positive photosensitive resin composition was applied onto ITO-glass using a spin coater, and then prebaked on a hot plate at a temperature of 100 ° C. for 120 seconds to form a coating film having a film thickness of 1.2 μm. This coating film was irradiated with ultraviolet rays having a light intensity of 5.5 mW / cm ² at 365 nm for a certain period of time by an ultraviolet irradiation device PLA-600FA manufactured by Canon Inc. through a mask having a line and space pattern of 15 μm. Then, it was developed by immersing it in a 0.4% TMAH aqueous solution for 60 seconds, and then washed with ultrapure water for 30 seconds. Next, the coating film on which this line-and-space pattern was formed was post-baked and cured by heating at a temperature of 230 ° C. for 30 minutes. The cross-sectional shape and opening residue of the cured line-and-space pattern were observed using a scanning electron microscope S-4800 manufactured by Hitachi High-Technologies Corporation. The results obtained are shown in Table 2.

Example 3, Examples 5-7
The positive photosensitive resin composition was applied onto ITO-glass using a spin coater, and then prebaked on a hot plate at a temperature of 100 ° C. for 120 seconds to form a coating film having a film thickness of 1.7 μm. This coating film was irradiated with ultraviolet rays having a light intensity of 5.5 mW / cm ² at 365 nm for a certain period of time by an ultraviolet irradiation device PLA-600FA manufactured by Canon Inc. through a mask having a line and space pattern of 15 μm. Then, it was developed by immersing it in a 2.38% TMAH aqueous solution for 20 seconds, and then washed with ultrapure water for 20 seconds. Next, the coating film on which this line-and-space pattern was formed was post-baked and cured by heating at a temperature of 230 ° C. for 30 minutes. The cross-sectional shape and opening residue of the cured line-and-space pattern were observed using a scanning electron microscope S-4800 manufactured by Hitachi High-Technologies Corporation. The results obtained are shown in Table 2.

Example 4
The positive photosensitive resin composition was applied onto ITO-glass using a spin coater, and then prebaked on a hot plate at a temperature of 100 ° C. for 120 seconds to form a coating film having a film thickness of 1.2 μm. This coating film was irradiated with ultraviolet rays having a light intensity of 5.5 mW / cm ² at 365 nm for a certain period of time by an ultraviolet irradiation device PLA-600FA manufactured by Canon Inc. through a mask having a line and space pattern of 15 μm. Then, it was developed by immersing it in a 1.0% TMAH aqueous solution for 120 seconds, and then washed with ultrapure water for 20 seconds. Next, the coating film on which this line-and-space pattern was formed was post-baked and cured by heating at a temperature of 230 ° C. for 30 minutes. The cross-sectional shape and opening residue of the cured line-and-space pattern were observed using a scanning electron microscope S-4800 manufactured by Hitachi High-Technologies Corporation. The results obtained are shown in Table 2.

[Evaluation of sensitivity]
Examples 1-2, Comparative Examples 1-2
A positive photosensitive resin composition was applied onto a silicon wafer using a spin coater, and then prebaked on a hot plate at a temperature of 100 ° C. for 120 seconds to form a coating film having a film thickness of 1.2 μm. This coating film was irradiated with ultraviolet rays having a light intensity of 5.5 mW / cm ² at 365 nm for a certain period of time by an ultraviolet irradiation device PLA-600FA manufactured by Canon Inc. Then, it was developed by immersing it in a 0.4% TMAH aqueous solution for 60 seconds, and then washed with ultrapure water for 30 seconds. The minimum exposure amount (mJ / cm ² ) at which no undissolved residue was left in the exposed portion was defined as the sensitivity. The results obtained are shown in Table 2.

Example 3, Examples 5-7
After the positive photosensitive resin composition was applied onto a silicon wafer using a spin coater, it was prebaked on a hot plate at a temperature of 100 ° C. for 120 seconds to form a coating film having a film thickness of 1.7 μm. This coating film was irradiated with ultraviolet rays having a light intensity of 5.5 mW / cm ² at 365 nm for a certain period of time by an ultraviolet irradiation device PLA-600FA manufactured by Canon Inc. Then, it was developed by immersing it in a 2.38% TMAH aqueous solution for 20 seconds, and then washed with ultrapure water for 20 seconds. The minimum exposure amount (mJ / cm ² ) at which no undissolved residue was left in the exposed portion was defined as the sensitivity. The results obtained are shown in Table 2.

Example 4
A positive photosensitive resin composition was applied onto a silicon wafer using a spin coater, and then prebaked on a hot plate at a temperature of 100 ° C. for 120 seconds to form a coating film having a film thickness of 1.2 μm. This coating film was irradiated with ultraviolet rays having a light intensity of 5.5 mW / cm ² at 365 nm for a certain period of time by an ultraviolet irradiation device PLA-600FA manufactured by Canon Inc. Then, it was developed by immersing it in a 1.0% TMAH aqueous solution for 120 seconds, and then washed with ultrapure water for 20 seconds. The minimum exposure amount (mJ / cm ² ) at which no undissolved residue was left in the exposed portion was defined as the sensitivity. The results obtained are shown in Table 2.

As shown in Table 2, in Examples 1 to 7, the sensitivity was high and the liquid repellency was also good. Furthermore, the pattern shape was also good, and it showed excellent characteristics that there was no residue in the opening.
On the other hand, in Comparative Examples 1 and 2, sufficient liquid repellency of anisole was not obtained after post-baking.

Claims (13)

A thermosetting positive photosensitive resin composition containing the following component (A), component (B), component (C) and solvent (D).
Component (A): At least one selected from a fluoroalkyl group having 3 to 10 carbon atoms, a polyfluoroether group, a silyl ether group and a polysiloxane group having a liquid repellent group and a quinonediazide group. The polymer that is the group of
(B) Ingredient: Alkali-soluble resin,
(C) Ingredient: 1,2-quinonediazide compound,
(D) Solvent. The positive photosensitive resin composition according to claim 1, further satisfying at least one of the following (Z1) and (Z2).
(Z1): Further contains a cross-linking agent which is a component (E).
(Z2): A group in which the alkali-soluble resin of the component (B) further has a self-crosslinkable group or reacts with at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group and an amino group. Have more. The positive photosensitive resin composition according to any one of claims 1 and 2 , wherein the polymer of the component (A) is an acrylic polymer. The positive photosensitive resin composition according to claim 3 , wherein the acrylic polymer of the component (A) has a number average molecular weight of 2,000 to 100,000 in terms of polystyrene. The positive photosensitive resin composition according to claim 3 or 4 , wherein the acrylic polymer of the component (A) further has a group selected from a carboxyl group and a phenolic hydroxyl group. The positive photosensitive resin composition according to any one of claims 1 to 5 , wherein the alkali-soluble resin of the component (B) has a number average molecular weight of 2,000 to 50,000 in terms of polystyrene. The positive photosensitive resin composition according to any one of claims 1 to 6 , wherein the component (A) is contained in an amount of 0.1 to 20 parts by mass with respect to 100 parts by mass of the component (B). .. The positive type according to any one of claims 1 to 7 , wherein the component (C) is 5 to 100 parts by mass with respect to a total of 100 parts by mass of the component (A) and the component (B). Photosensitive resin composition. The invention according to any one of claims 1 to 8 , wherein the component (E) is 1 to 50 parts by mass with respect to 100 parts by mass of the total of the component (A) and the component (B). Positive type photosensitive resin composition. Claims 1 to 9 , wherein the defoaming agent is further contained as the component (F) in an amount of 0.01 to 1.0 mass with respect to a total of 100 parts by mass of the component (A) and the component (B). The positive photosensitive resin composition according to any one of the above. A cured film obtained by using the positive photosensitive resin composition according to any one of claims 1 to 10 . The display element having the cured film according to claim 11 . A display element having the cured film according to claim 11 as an image forming lower layer film.