JP7324581B2 - Bank pattern formation method - Google Patents

Description

The present invention relates to a method for forming a bank pattern of a cured film obtained from a photosensitive resin composition. The method of forming a bank pattern of a cured film using this photosensitive resin composition is particularly suitable as a method of forming an interlayer insulating film in a liquid crystal display or an EL display, or a light-shielding wall or partition compatible with an inkjet method.

2. Description of the Related Art In recent years, techniques for producing full-color display substrates using inkjet have been actively investigated in the process of producing display elements such as thin film transistor (TFT) type liquid crystal display elements and organic EL (electroluminescent) elements. For example, regarding the production of color filters in liquid crystal display elements, in contrast to the conventional printing method, electrodeposition method, dyeing method, or pigment dispersion method, pre-patterned sections defining pixels (hereinafter referred to as banks) are shielded from light. A color filter formed of a photosensitive resin layer, in which ink droplets are dropped onto a region surrounded by banks, and a method for manufacturing the same (Patent Document 1) have been proposed. Also in the case of organic EL display elements, a method has been proposed (Patent Document 2) in which a bank is prepared in advance and an ink that will form a light-emitting layer is similarly dropped to prepare an organic EL display element (Patent Document 2).

For the purpose of increasing contrast and improving visibility in an organic EL display device, an attempt has been made to add a pigment to a bank material to impart a light-shielding property. Also, attempts have been made to mix fine particles into the bank material for the purpose of improving the resolution of the bank material. Attempts have also been made to mix fine particles for the purpose of improving the refractive index and transparency of the photosensitive resin composition. However, all of these methods have the problem that residues of added pigments and fine particles remain in pattern openings, causing defects in organic EL display devices.

As a method for suppressing the residue in the opening of the bank, a layer containing a hydrophilic compound is provided as a lower layer of the bank material having liquid repellency, and is removed together with the upper layer of the bank material by development. Methods have been proposed to prevent contamination of bank openings that should have . However, in this method, since the lower layer is highly hydrophilic, moisture absorption tends to occur, and there are problems such as peeling of the pattern.

As a method for suppressing the residue in the opening of the bank, an organic layer is provided as a lower layer of a liquid-repellent bank material, a pattern is formed with the upper layer of the bank material, and then the lower layer is removed by a dry etching process to form a bank opening. A method for improving the lyophilicity of is proposed (Patent Document 8). However, this method has a problem that the process becomes complicated.

In addition, Patent Documents 9 and 10 propose a method of forming a pattern by performing one exposure process and one development process on two laminated organic layers. However, none of these are aimed at suppressing residues in pattern openings. Further, in the method of Patent Document 9, since the underlying organic layer does not have photosensitivity, precise process control is required to control the pattern dimensions. In the method of Patent Document 10, it was necessary to perform heat treatment after the exposure process, and the process was complicated.

JP-A-2000-187111 JP-A-11-54270 JP-A-2000-353594 JP-A-10-197715 JP 2010-33925 A JP 2010-73340 A JP 2010-129344 A JP 2011-216250 A Japanese Patent No. 4182358 Japanese Patent No. 5083566

Even if a bank containing a pigment or fine particles that can improve the performance of a display element or a liquid-repellent bank that is simple in process and advantageous in terms of production cost is used, the pigment or fine particles can be used in areas other than the bank. and a method for forming a bank pattern in which residues such as components of a liquid-repellent resist material are less likely to remain.

The present inventors provided an underlayer film by coating a first photosensitive resin composition containing an alkali-soluble resin having an amide group directly or via another layer on a substrate, and on the underlayer film, A second photosensitive resin composition containing a liquid-repellent polymer and fine particles is applied to form a resist film, and the resist film is exposed and developed to form a bank. In this development process, the lower layer film in the non-bank areas is removed together with the resist film in the non-bank areas, thereby reducing the resist film residue containing lyophobic components and fine particles on the substrate and improving the lyophilicity of the openings. The inventors have found that water repellency and liquid repellency can be efficiently imparted to the film surface while maintaining the properties, and have completed the present invention.
Here, the region where the bank is located on the substrate is called the bank portion, and the region other than the bank is called the non-bank portion.

That is, the present invention relates to the following.
1. In a method for forming banks and regions defined by the banks on a substrate, the method for forming a bank pattern for forming an organic thin film in the regions defined by the banks, comprising:
Underlayer film formation by coating a first photosensitive resin composition containing the following components (A), (C) and (D) on a substrate directly or via another layer to provide an underlayer film process and
A resist film forming step of applying a second photosensitive resin composition containing the following components (a), (b), (c) and (d) on the underlayer film to form a resist film. and,
a bank forming step of forming banks by exposing and developing the resist film, and removing the lower layer film in the non-bank portions together with the resist film in the non-bank portions during the developing process.
(A) component: an alkali-soluble resin having an amide group,
(C) component: solvent,
(D) component: photosensitizer,
(a) component: alkali-soluble resin,
(b) component: fine particles,
(c) component: solvent,
(d) Component: Photosensitizer.
2. 2. The method for forming a bank pattern according to 1 above, wherein the component (b) is inorganic fine particles.
3. 2. The method for forming a bank pattern according to 1 above, wherein the component (b) is fine particles containing a coloring agent. 4. 4. The method for forming a bank pattern according to any one of 1 to 3 above, wherein the component (b) has an average particle size of 5 nm to 1000 nm.
5. 5. The method for forming a bank pattern according to any one of 1 to 4 above, wherein the first photosensitive resin composition satisfies at least one of the following (Z1) to (Z4).
(Z1): further containing a cross-linking agent as component (E);
(Z2): The alkali-soluble resin having an amide group of component (A) further has a self-crosslinking group or at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group and an amino group. further having reactive groups;
(Z3): a photoradical generator in which component (D) is (D-2), and further contains a compound having two or more ethylenic double bonds as component (F);
(Z4): A photoacid generator in which the (D) component is (D-3), and further, as the (G) component, two or more functional groups that form a covalent bond with the acid generated from the (D) component. 6. containing a compound having 6. The method for forming a bank pattern according to any one of 1 to 5 above, wherein the second photosensitive resin composition satisfies at least one of the following (z1) to (z4). (z1): further containing a cross-linking agent as component (e);
(z2): The alkali-soluble resin of component (a) further has a self-crosslinking group or a group that reacts with at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group and an amino group. further have;
(z3): a photoradical generator in which component (d) is (d-2), and further contains a compound having two or more ethylenic double bonds as component (f);
(z4): a photoacid generator in which the (d) component is (d-3), and as the (g) component, two or more functional groups that form a covalent bond with the acid generated from the (d) component. 7. containing a compound having 5. The method for forming a bank pattern according to any one of 1 to 4 above, wherein the component (D) and/or (d) is a quinonediazide compound.
8. 6. The method for forming a bank pattern as described in 5 above, wherein component (D) is a quinone diazide compound and further satisfies (Z1) and/or (Z2).
9. 7. The method for forming a bank pattern as described in 6 above, wherein the component (d) is a quinonediazide compound and further satisfies any one of the above (z1) and/or (z2).
10. 8. The method for forming a bank pattern as described in 8 above, wherein the component (D) is diazonaphthoquinone.
11. 9. The method for forming a bank pattern as described in 9 above, wherein the component (d) is diazonaphthoquinone.
12. 12. The method for forming a bank pattern according to any one of 1 to 11 above, wherein the second photosensitive resin composition further contains the following component (h).
(h) component: a polymer having a liquid-repellent group (h1),
13. 13. The method for forming a bank pattern as described in 12 above, wherein the component (h) further comprises a polymer having the following (h2).
(h2): at least one group selected from N-alkoxymethylamide groups, blocked isocyanate groups and trialkoxysilyl groups.
14. 14. The method of forming a bank pattern as described in 12 or 13 above, wherein the component (h) further comprises a polymer having the following (h3).
(h3): at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group and an amino group;
15. At least the liquid-repellent group (h1) of component (h) is selected from the group consisting of a fluoroalkyl group having 3 to 10 carbon atoms, a polyfluoroether group, a silyl ether group and a polysiloxane group represented by Formula 5 15. The method for forming a bank pattern according to any one of 12 to 14 above, which is a kind of group.
—(SiR ¹ R ² —O) _n —SiR ¹ R ² R ³ Formula 5
(where R ¹ and R ² independently represent a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group; R ³ represents hydrogen or an organic group having 1 to 10 carbon atoms; n is an integer of 1 to 200; represents ).
16. 16. The method for forming a bank pattern according to any one of 12 to 15 above, wherein the polymer of component (h) is an acrylic polymer.
17. 17. The method for forming a bank pattern as described in 16 above, wherein the acrylic polymer of component (h) has a number average molecular weight of 2,000 to 100,000 in terms of polystyrene.
18. Forming a bank pattern according to any one of items 12 to 17 above, wherein 0.1 to 20 parts by mass of component (h) is contained in 100 parts by mass of component (a). Method.
19. 12. The method for forming a bank pattern according to any one of 1 to 11 above, wherein component (a) is a resin having a liquid-repellent group (h1) and component (h) is not contained.
20. The method for forming a bank pattern as described in 19 above, wherein polymer units having a liquid-repellent group (h1) account for 5 to 30 parts by weight in 100 parts by weight of component (a).
21. 21. Any one of 1 to 20 above, wherein the alkali-soluble resin having an amide group as component (A) and/or the alkali-soluble resin as component (a) has a number average molecular weight of 2,000 to 50,000 in terms of polystyrene. 3. The method of forming a bank pattern according to .
22. 22. The method of forming a bank pattern according to any one of the above items 1 to 21, wherein component (b) is contained in an amount of 5 to 500 parts by mass with respect to 100 parts by mass of component (a).
23. 23. The method for forming a bank pattern as described in any one of 5 to 22 above, wherein component (E) is 1 to 50 parts by mass per 100 parts by mass of component (A).
24. 24. The method of forming a bank pattern according to any one of the above 1 to 23, wherein the other layer is an organic electroluminescent hole injection layer.
25. 25. A cured film formed by the method for forming a bank pattern according to any one of 1 to 24 above.
26. 26. A display device comprising the cured film as described in 25 above.
27. 26. A display device having the cured film as described in 25 above as an image forming partition.
28. A photosensitive resin composition for forming an underlayer film of a resist film, containing the following components (A), (C) and (D).
(A) component: an alkali-soluble resin having an amide group,
(C) component: solvent,
(D) Component: Photosensitizer.

According to the method of forming a bank pattern of the present invention, even if a bank containing pigments or fine particles that can improve the performance of a display element or a liquid-repellent bank that is simple in process and advantageous in terms of production cost is used, A bank pattern that improves the lyophilicity of the substrate surface can be formed by suppressing the residue of the resist material such as the lyophobic component and fine particles on the substrate surface in the non-bank portion. In other words, a uniform organic thin film can be formed within the regions partitioned by the banks.

FIG. 1 is a schematic cross-sectional view showing a manufacturing method for forming banks and regions partitioned by the banks on a substrate.

Details of the bank pattern forming method of the present invention will be described below.
A method of forming a bank pattern of the present invention is a method of forming banks and regions partitioned by the banks on a substrate, and forming a bank pattern for forming an organic thin film in the regions partitioned by the banks. in the method
Underlayer film formation by coating a first photosensitive resin composition containing the following components (A), (C) and (D) on a substrate directly or via another layer to provide an underlayer film process and
A resist film forming step of applying a second photosensitive resin composition containing the following components (a), (b), (c) and (d) on the underlayer film to form a resist film. and,
a bank forming step of forming banks by exposing and developing the resist film, and removing the underlying film in the non-bank portions together with the resist film in the non-bank portions during the developing process; be.
(A) component: alkali-soluble resin having an amide group (C) component: solvent (D) component: photosensitive agent (a) component: alkali-soluble resin (b) component: fine particles (c) component: solvent (d) component: photosensitizer

In the second photosensitive resin composition of the present invention, the component (b) is preferably inorganic fine particles.
In the second photosensitive resin composition of the present invention, the component (b) is preferably fine particles containing a colorant.
In the second photosensitive resin composition of the present invention, the component (b) preferably has an average particle size of 1 nm to 1000 nm.

The first photosensitive resin composition of the present invention preferably further satisfies at least one of the following (Z1) to (Z4).
(Z1): further containing a cross-linking agent as component (E);
(Z2): The alkali-soluble resin having an amide group of component (A) further has a self-crosslinking group or at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group and an amino group. further having reactive groups;
(Z3): a photoradical generator in which the component (D) is (D-2), and further contains a compound having two or more ethylenically polymerizable groups as the component (F);
(Z4): A photoacid generator in which the (D) component is (D-3), and as the (G) component, two functional groups that form a covalent bond with the acid generated from the (D-3) component. Contains compounds with one or more

The second photosensitive resin composition of the present invention preferably further satisfies at least one of the following (z1) to (z4).
(z1): further containing a cross-linking agent as component (e);
(z2): The alkali-soluble resin of component (a) further has a self-crosslinking group or a group that reacts with at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group and an amino group. further have;
(z3): a photoradical generator in which component (d) is (d-2), and further contains a compound having two or more ethylenically polymerizable groups as component (f);
(z4): A photoacid generator in which the (d) component is (d-3), and as the (g) component, two functional groups that form a covalent bond with the acid generated from the (d-3) component. Contains compounds with one or more

The photosensitive resin composition of the present invention is preferably a positive photosensitive resin composition in which component (D) and/or component (d) is diazonaphthoquinone.

A method of forming a bank pattern according to the present invention will be described below with reference to FIG.

<Lower layer film forming process>
In the manufacturing method of the present invention, first, a first photosensitive resin composition composed of a monomer having an amide group and a monomer having an alkali-soluble group, which will be described later, is applied directly or via another layer to the substrate 11 and prebaked. Then, a lower layer film 12 having no liquid repellency is provided.

Details of each component of the underlayer film will be described below.

<(A) Component>
The (A) component of the present invention is an alkali-soluble resin having an amide group. By having an amide group, hydrogen bonds can be formed in molecules or between molecules, and when an upper layer resist film, which will be described later, is applied, solvent resistance to the solvent can be exhibited. The upper layer resist film does not come into contact with the substrate at the time of application. The resin of component (A) contains an alkali-soluble group for imparting alkali-solubility. Phosphate groups, boronate groups, and active methylene and methine groups are included. The phenolic hydroxy group and carboxyl group are not only alkali-soluble groups, but also heat-reactive sites (sites capable of forming a cross-linked structure with the cross-linking agent of component (E)) as described later.
Component (A) is not particularly limited in terms of other structures and contained functional groups as long as it is an alkali-soluble resin having the above amide group. For example, when containing a compound having two or more functional groups that form a covalent bond with an acid (G), which will be described later, the component (A) may not have a reaction site with the component (G), or the component (G ) When it has a reactive site with component (G), the reactive site may be a group capable of forming a covalent bond with component (G) by the action of an acid, or a group capable of forming a covalent bond with component (G) by heating. is not particularly limited.

Here, the active methylene group means a methylene group ( _--CH.sub.2-- ) having a carbonyl group at an adjacent position and having reactivity with a nucleophilic reagent. In the present invention, the active methine group refers to the active methylene group having a structure in which one hydrogen atom of the methylene group is substituted with an alkyl group and having reactivity with a nucleophilic reagent.

（式（Ａ１）中、Ｒはアルキル基、アルコキシ基又はフェニル基を表し、破線は結合手を表す。） Among active methylene groups and active methine groups, active methylene groups are preferred, and active methylene groups represented by the following formula (A1) are more preferred.

(In formula (A1), R represents an alkyl group, an alkoxy group, or a phenyl group, and a dashed line represents a bond.)

In the above formula (A1), the alkyl group represented by R includes, for example, an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 5 carbon atoms.
Examples of such alkyl groups include methyl group, ethyl group, n-propyl group, i-propyl group and the like.
Among them, a methyl group, an ethyl group, an n-propyl group and the like are preferable.

In the above formula (A1), the alkoxy group represented by R includes, for example, an alkoxy group having 1 to 20 carbon atoms, preferably an alkoxy group having 1 to 5 carbon atoms.
Examples of such alkoxy groups include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy and t-butoxy groups.
Among them, methoxy group, ethoxy group, i-propoxy group, n-propoxy group and the like are preferable.

Examples of the group represented by formula (A1) include the following structures. In the structural formulas, dashed lines represent bonds.

Among the alkali-soluble resins of the component (A), it has an amide group, has at least one group selected from the group consisting of a phenolic hydroxy group and a carboxyl group as an alkali-soluble group, and has a number average molecular weight. of 2,000 to 50,000 is preferred.

The alkali-soluble resin of the component (A) may be any alkali-soluble resin having such a structure, and there are no particular restrictions on the type of backbone and side chains of the polymer constituting the resin.

However, the alkali-soluble resin of component (A) has a number average molecular weight within the range of 2,000 to 50,000. If the number average molecular weight is too large, exceeding 50,000, development residues are likely to occur, and the sensitivity is greatly reduced. At that time, a considerable amount of film loss occurs in the exposed area, which may result in insufficient curing.

(A) Component alkali-soluble resins include, for example, acrylic resins, polyhydroxystyrene resins, polyimide precursors, polyimides, and the like. Among them, acrylic resin (acrylic polymer) can be mentioned as a preferable resin.

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

That is, the above specific copolymer contains at least one group selected from the group consisting of a carboxyl group and a phenolic hydroxy group as a monomer exhibiting alkali solubility, that is, a suitable alkali-soluble group, together with a monomer having an amide group. and optionally at least one monomer selected from the group of monomers copolymerizable with these monomers as essential structural units, the copolymer having a number average molecular weight of 2,000 from 50,000. A number average molecular weight greater than 50,000 may result in residue.
In addition, the monomer having an amide group may have an alkali-soluble group at the same time.

Monomers having the above amide groups are, for example, acrylamide, methacrylamide, N
-methylacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, N-phenylmethacrylamide, N-phenylacrylamide, 4-hydroxyphenylmethacrylamide, 4-hydroxyphenylacrylamide and the like, which may be used alone or Two or more kinds can be used in combination. Among them, methacrylamide is preferred.

The "monomer having at least one selected from the group consisting of a carboxyl group and a phenolic hydroxy group" includes monomers having a carboxyl group and monomers having a phenolic hydroxy group. These monomers are not limited to having one carboxyl group or phenolic hydroxy group, and may have a plurality of them.

Specific examples of the above monomers are listed below, but are not limited to these.
Examples of monomers having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, mono-(2-(acryloyloxy)ethyl) phthalate, mono-(2-(methacryloyloxy)ethyl) phthalate, N-(carboxyphenyl ) maleimide, N-(carboxyphenyl)methacrylamide, N-(carboxyphenyl)acrylamide and the like.

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

In the production of the component (A) alkali-soluble resin (specific copolymer), the proportion of monomers exhibiting alkali solubility, for example, the proportion of monomers having at least one group selected from the group consisting of carboxyl groups and phenolic hydroxy groups The ratio is preferably 5% by mass or more, more preferably 10% by mass or more, of all the monomers used for producing the component (A) alkali-soluble resin (specific copolymer). When the monomer exhibiting alkali solubility (monomer having at least one group selected from the group consisting of a carboxyl group and a phenolic hydroxy group) is less than 5% by mass, alkali solubility of the alkali-soluble resin (acrylic polymer) Lack of sexuality.

In the component (A), the alkali-soluble resin, the amount of amide groups introduced is preferably 5 to 60% by mass, more preferably 5 to 40% by mass, based on the total repeating units. For example, in the production of the specific copolymer, the ratio of the monomer having an amide group to all the monomers used in the production of the specific copolymer can be, for example, 5 to 40% by mass.

The alkali-soluble resin, which is the component (A) 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 preferred.

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

In the production of component (A) alkali-soluble resin (specific copolymer), when using a monomer having a hydroxyalkyl group and a polymerizable unsaturated group, the ratio It is preferably 5% to 60% by weight, more preferably 10% to 50% by weight, and most preferably 20% to 40% by weight, relative to the monomer. If the amount of the monomer having a hydroxyalkyl group and a polymerizable unsaturated group is less than 5% by mass, the effect of stabilizing the pattern shape of the copolymer may not be obtained. If the amount is 60% by mass or more, the proportion of the alkali-soluble group in the component (A) is insufficient, and properties such as developability may deteriorate.

The alkali-soluble resin, which is the component (A) of the present invention, can be further copolymerized with an N-substituted maleimide compound in order to raise the Tg of the copolymer.

Examples of N-substituted maleimide compounds include N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, and the like. A compound having no aromatic ring is preferred from the viewpoint of transparency, and a compound having an alicyclic skeleton is more preferred from the viewpoint of developability, transparency and heat resistance, and cyclohexylmaleimide is most preferred.

When the N-substituted maleimide is used in the production of the alkali-soluble resin (specific copolymer) of component (A), the ratio is preferably 5 to 60 mass with respect to all the monomers used in the production of the specific copolymer. %, more preferably 10% by mass to 50% by mass. If the N-substituted maleimide is less than 5% by mass, the effect of improving the Tg of the copolymer may not be obtained. If it is 60% by mass or more, the solubility in the solvent may decrease.

When the first photosensitive resin composition of the present invention satisfies the requirement (Z2), the alkali-soluble resin (A) used in the present invention further has a self-crosslinking group, or has a hydroxy group, a carboxyl group, 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 an amide group and an amino group. For example, the requirement (Z2) can be satisfied by introducing a repeating unit having at least one group selected from the group consisting of self-crosslinkable groups and crosslinkable groups into the alkali-soluble resin (A). .

Examples of the self-crosslinkable groups include N-alkoxymethyl groups, N-hydroxymethyl groups, alkoxysilyl groups, epoxy groups, oxetanyl groups, vinyl groups and blocked isocyanate groups.

Examples of the crosslinkable groups include N-alkoxymethyl groups, N-hydroxymethyl groups, alkoxysilyl groups, epoxy groups, vinyl groups, blocked isocyanate groups and the like.

When the self-crosslinking group or crosslinkable group is contained in the alkali-soluble resin of component (A), the content of the self-crosslinkable group or crosslinkable group is based on the total of all repeating units in the resin of component (A). It preferably contains 10% to 70% by mass, particularly preferably 20% to 60% by mass, of units having a functional group.

The alkali-soluble resin of component (A) further includes self-crosslinking groups such as N-alkoxymethyl groups, N-hydroxymethyl groups, alkoxysilyl groups, epoxy groups, oxetanyl groups, vinyl groups and blocked isocyanate groups, and N-alkoxy groups. When having a repeating unit having at least one selected from crosslinkable groups such as a methyl group, an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, a vinyl group, and a blocked isocyanate group, for example, it has radical polymerizability, An unsaturated compound having at least one selected from crosslinkable groups such as epoxy groups, oxetanyl groups, vinyl groups and blocked isocyanate groups, and self-crosslinkable groups such as N-alkoxymethyl groups, N-hydroxymethyl groups and alkoxysilyl groups. (monomer) may be copolymerized.

Monomers having radical polymerizability and having an N-alkoxymethyl group include N-butoxymethylacrylamide, N-isobutoxymethylacrylamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, N-methylolacrylamide and the like. mentioned.

Examples of monomers having radical polymerizability and having an N-hydroxymethyl group include N-hydroxymethylacrylamide and N-hydroxymethylmethacrylamide.

Examples of monomers having radical polymerizability and having an alkoxysilyl group include 3-acryloyloxytrimethoxysilane, 3-acryloyloxytriethoxysilane, 3-methacryloyloxytrimethoxysilane, 3-methacryloyloxytriethoxysilane, and the like. mentioned.

Examples of radically polymerizable monomers having an epoxy group include glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 3,4-epoxycyclohexyl methacrylate, 6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl methacrylate, α-ethyl acrylate-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether and the like. Among these, glycidyl methacrylate, 6,7-epoxyheptyl methacrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3,4-epoxycyclohexyl methacrylate, etc. It is preferably used. These are used singly or in combination.

Examples of the radically polymerizable monomer having an oxetanyl group include (meth)acrylic acid esters having an oxetanyl group. In this specification, the term "(meth)acrylic acid" refers to both acrylic acid and methacrylic acid.
Among such monomers are 3-(methacryloyloxymethyl)oxetane, 3-(acryloyloxymethyl)oxetane, 3-(methacryloyloxymethyl)-3-ethyl-oxetane, 3-(acryloyloxymethyl)-3- ethyl-oxetane, 3-(methacryloyloxymethyl)-2-trifluoromethyloxetane, 3-(acryloyloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloyloxymethyl)-2-phenyl-oxetane, 3- (acryloyloxymethyl)-2-phenyl-oxetane, 2-(methacryloyloxymethyl)oxetane, 2-(acryloyloxymethyl)oxetane, 2-(methacryloyloxymethyl)-4-trifluoromethyloxetane, 2-(acryloyloxy) Methyl)-4-trifluoromethyloxetane is preferred, and 3-(methacryloyloxymethyl)-3-ethyl-oxetane, 3-(acryloyloxymethyl)-3-ethyl-oxetane and the like are preferably used.

Monomers having radical polymerizability and having a vinyl group include 2-(2-vinyloxyethoxy)ethyl acrylate and 2-(2-vinyloxyethoxy)ethyl methacrylate.

As a monomer having radical polymerizability and a blocked isocyanate group,
2-(0-(1'-methylpropylideneamino)carboxyamino)ethyl methacrylate, 2-(3,5-dimethylpyrazolyl)carbonylamino)ethyl methacrylate and the like.

When the first photosensitive resin composition of the present invention satisfies (Z2), it has radical polymerizability and contains an N-alkoxymethyl group, N-hydroxymethyl group, alkoxysilyl group, epoxy group, oxetanyl group, vinyl At least one group selected from self-crosslinkable groups such as groups and blocked isocyanate groups, and crosslinkable groups such as N-alkoxymethyl groups, N-hydroxymethyl groups, alkoxysilyl groups, epoxy groups, vinyl groups, and blocked isocyanate groups Preferably 10% by mass to 70% by mass, particularly preferably 20% by mass, based on the total of all repeating units of the alkali-soluble resin (A), the structural unit derived from a monomer (unsaturated compound) having to 60% by mass. If the amount of this structural unit is less than 10% by mass, the heat resistance and surface hardness of the resulting cured film tend to decrease. It tends to be less stable.

In the present invention, the component (A) alkali-soluble resin (a specific copolymer, such as an acrylic polymer) is also formed of monomers other than the above monomers (hereinafter referred to as other monomers) as structural units. It may be a copolymer. Other monomers, specifically, may be copolymerizable with at least one selected from the group consisting of the above-mentioned monomers having a carboxyl group and monomers having a phenolic hydroxyl group. It is not particularly limited as long as it does not damage it. Specific examples of such monomers include acrylic acid ester compounds, methacrylic acid ester compounds, N-substituted acrylamide compounds, maleimide, acrylonitrile, styrene compounds and vinyl compounds.
Specific examples of the other monomer are listed below, but are not limited thereto.

Examples of the acrylic ester compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, glycidyl acrylate, 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, γ-butyrolactone acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, 8-ethyl-8-tricyclodecyl acrylate, diethylene glycol mono acrylates, caprolactone 2-(acryloyloxy)ethyl ester, poly(ethylene glycol) ethyl ether acrylate, and the like.

Examples of the methacrylate compounds 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, 8-ethyl-8-tricyclodecyl methacrylate, diethylene glycol monomethacrylate, caprolactone 2-(methacryloyloxy)ethyl ester, poly(ethylene glycol) ethyl ether methacrylate, and the like.

Examples of the N-substituted acrylamide compounds include N-methylacrylamide, N-methylmethacrylamide, N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, N-butoxymethylacrylamide, N-butoxymethylmethacrylamide and the like.

Examples of the styrene compound include styrene having no hydroxyl group, such as styrene, α-methylstyrene, chlorostyrene, and bromostyrene.

Examples of the vinyl compound include methyl vinyl ether, benzyl vinyl ether, cyclohexyl vinyl ether, vinylnaphthalene, vinylanthracene, vinylcarbazole, allyl glycidyl ether, 3-ethenyl-7-oxabicyclo[4.1.0]heptane, 1,2 -epoxy-5-hexene and 1,7-octadiene monoepoxide.

In the production of the alkali-soluble resin (specific copolymer) that is the component (A), the ratio of the other monomers is preferably 80% by mass or less with respect to all the monomers used in the production of the specific copolymer. , more preferably 50% by mass or less, and still more preferably 20% by mass or less. If it exceeds 80% by mass, the amount of essential components (essential monomers constituting component (A)) is relatively reduced, making it difficult to sufficiently obtain the effects of the present invention.

The method for obtaining the alkali-soluble resin (specific copolymer), which is the component (A) used in the present invention, is not particularly limited. , a monomer having at least one group selected from phenolic hydroxy groups and the like, and optionally a monomer having a hydroxyalkyl group, an N-substituted maleimide compound, and optionally an N-alkoxymethyl group, an N-hydroxymethyl group, self-crosslinking groups such as alkoxysilyl groups, epoxy groups, oxetanyl groups, vinyl groups and blocked isocyanate groups; Polymerization reaction at a temperature of 50 to 110° C. in a solvent in which a monomer having at least one group selected from crosslinkable groups, optionally other copolymerizable monomers, and optionally a polymerization initiator, etc. coexist. It is obtained by At that time, the solvent used is not particularly limited as long as it dissolves the monomers constituting the alkali-soluble resin (specific copolymer) and the alkali-soluble resin (specific copolymer). Specific examples thereof include solvents described in component (C) described later.

The component (A) alkali-soluble resin (specific copolymer) thus obtained is usually in the form of a solution dissolved in a solvent. In the present invention, the obtained solution of the alkali-soluble resin (specific copolymer) of component (A) may be used as it is for the preparation of the photosensitive resin composition described below.

In addition, the solution of the alkali-soluble resin (specific copolymer) of the component (A) obtained as described above is added to diethyl ether, water, or the like while stirring to reprecipitate, and the formed precipitate is filtered. - After washing, the specific copolymer can be powdered by drying at room temperature or by heating under normal pressure or reduced pressure. By such an operation, the polymerization initiator and unreacted monomers coexisting with the specific copolymer can be removed, and as a result, a purified powder of the specific copolymer can be obtained. If the purification cannot be sufficiently performed in 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 as the alkali-soluble resin of the component (A), or the powder may be re-dissolved in the component (C) described later to form a solution. may be used as

Further, as the alkali-soluble resin of component (A), polyimide precursors such as polyamic acid, polyamic acid ester, partially imidized polyamic acid, and polyimides such as carboxylic acid group-containing polyimides can be used. As long as it is soluble, it can be used without particular limitation on its type.

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

The above (a) tetracarboxylic dianhydride compound is not particularly limited, and specific examples include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3' ,4,4′-benzophenonetetracarboxylic dianhydride, 3,3′,4,4′-diphenyl ether tetracarboxylic dianhydride, 3,3′,4,4′-diphenylsulfonetetracarboxylic dianhydride aromatic tetracarboxylic acids such as; 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 Carboxylic acid dianhydrides, alicyclic tetracarboxylic acid dianhydrides such as 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic acid dianhydride; 1,2,3,4 Aliphatic tetracarboxylic dianhydrides such as -butanetetracarboxylic dianhydride can be mentioned.
These may be used singly or in combination of two or more.

The diamine compound (j) is also not particularly limited, and examples thereof include 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, and 4,6-diamino-1. , 3-benzenedicarboxylic 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- diamine compounds having a carboxyl group such as 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-hydroxy phenyl)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)methane, 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)hexafluoropropane, 4,4'-diamino-3,3'-dihydroxybiphenyl, 4,4'- Diamino-3,3′-dihydroxy-5,5′-dimethylbiphenyl, 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]sulfone, bis[4-(3-amino-4-hydroxyphenoxy)phenyl]propane, 2,2-bis[4 -Diamine compounds having a phenolic hydroxy group such as (3-amino-4-hydroxyphenoxy)phenyl]hexafluoropropane; 1,3-diamino-4-mercaptobenzene, 1,3-diamino-5-mercaptobenzene, 1 ,4-diamino-2-mercaptobenzene, bis(4-amino-3-mercaptophenyl)ether, 2,2-bis(3-amino-4-mercaptophenyl)hexafluoropropane and other diamine compounds having a thiophenol group ; 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, 4,4′-diamino-3,3′-dimethylbiphenyl-6,6′-disulfonic acid, and other diamine compounds having a sulfonic acid group. be done. 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- tolidine, m-tolidine, 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 -toluyl)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, etc. compounds can be mentioned.
These may be used singly or in combination of two or more.

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

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

In the production of polyamic acid, the reaction temperature for the reaction between the diamine compound and the tetracarboxylic dianhydride compound can be selected from -20 to 150°C, preferably from -5 to 100°C. In order to obtain polyamic acid having a high molecular weight, 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 a reaction temperature of 40° C. to 90° C. and a reaction time of 10 hours or longer.
When the terminal amino group is protected with an acid anhydride, the reaction temperature can be selected from -20 to 150°C, preferably from -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 that time include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, N-methylcaprolactam, dimethylsulfoxide, and tetramethylurea. , pyridine, dimethylsulfone, hexamethylsulfoxide, m-cresol, γ-butyrolactone, ethyl acetate, butyl acetate, ethyl lactate, methyl 3-methoxypropionate, methyl 2-methoxypropionate, ethyl 3-methoxypropionate, 2- ethyl methoxypropionate, ethyl 3-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, methyl isobutyl ketone, 2-heptanone and the like can be mentioned. These may be used alone or in combination. Furthermore, even a solvent that does not dissolve the polyamic acid may be mixed with the above solvent and used as long as the polyamic acid produced by the polymerization reaction is not precipitated.

The solution containing polyamic acid thus obtained can be used as it is for the preparation of a photosensitive resin composition. Alternatively, the polyamic acid can be precipitated and isolated in a poor solvent such as water, methanol, ethanol, etc., and then recovered and used.

Any polyimide can also be used as the component (A). The polyimide used in the present invention is obtained by chemically or thermally imidizing 50% or more of a polyimide precursor such as polyamic acid.

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

Such a polyimide can be obtained by synthesizing a polyimide precursor such as the polyamic acid described above, followed by chemical imidization or thermal imidization.
As a chemical imidization method, 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. As a thermal imidization method, a method of heating a polyimide precursor solution at a temperature of 180° C. to 250° C. while dehydrating it is generally used.

Phenol novolac resin can also be used as the alkali-soluble resin of component (A).

Moreover, polyester polycarboxylic acid can also be used as alkali-soluble resin of (A) component. A polyester polycarboxylic acid can be obtained from an acid dianhydride and a diol by the method described in WO 2009/051186.
Examples of acid dianhydrides include the above (i) tetracarboxylic dianhydrides.
Diols include aromatic diols such as bisphenol A, bisphenol F, 4,4'-dihydroxybiphenyl, benzene-1,3-dimethanol and benzene-1,4-dimethanol; hydrogenated bisphenol A and hydrogenated bisphenol F , 1,4-cyclohexanediol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol; and ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol. and other aliphatic diols.

In the present invention, the component (A) alkali-soluble resin may be a mixture of a plurality of alkali-soluble resins.

<(C) Component>
Component (C) used in the present invention dissolves component (A) as a solvent and, if necessary, component (D), component (E), component (F), and component (G) described below, and optionally It dissolves other additives to be added, which will be described later, and the type and structure of the solvent are not particularly limited as long as the solvent has such a dissolving ability.

Examples of such component (C) 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, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-butanone, 3-methyl-2-pentanone, 2-pentanone, 2-heptanone, γ-butyrolactone , ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate , ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N,N-dimethylformamide, N,N-dimethylacetamide, and and N-methylpyrrolidone.

These solvents can be used singly or in combination of two or more.
Among these (C) components, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 2-heptanone, propylene glycol propyl ether, propylene glycol propyl ether acetate, ethyl lactate, butyl lactate, etc. have good coating properties and are safe. Propylene glycol monomethyl ether, propylene glycol propyl ether, ethyl lactate, butyl lactate and the like are particularly preferred from the viewpoint of solubility of the component (A). These solvents are commonly used as solvents for photoresist materials.

<(D) Component>
Examples of the photosensitive agent (D) include (D-1) a 1,2-quinonediazide compound, (D-2) a photoradical generator, and (D-3) a photoacid generator.

(D-1) The 1,2-quinonediazide compound includes either a hydroxy group or an amino group, or a compound having both a hydroxy group and an amino group, and these hydroxy groups or amino groups (hydroxy group and If it has both amino groups, preferably 10 mol% to 100 mol%, particularly preferably 20 mol% to 95 mol% of the total amount thereof) is esterified with 1,2-quinonediazide sulfonic acid, or Amidated compounds can be used.
Examples of the 1,2-quinonediazide sulfonic acids include 1,2-naphthoquinone-2-diazide-5-sulfonic acid, 1,2-naphthoquinone-2-diazide-4-sulfonic acid, 1,2-benzoquinone-2- Chlorides of 1,2-quinonediazide sulfonic acid can be used in the reaction with compounds having either or both of a hydroxyl group and an amino group, such as diazido-4-sulfonic acid.
As the 1,2-quinonediazide compound (D-1), diazonaphthoquinone can be used.

Examples of compounds having a hydroxy group include phenol, o-cresol, m-cresol, p-cresol, hydroquinone, resorcinol, catechol, methyl gallate, ethyl gallate, 1,3,3-tris(4-hydroxyphenyl ) butane, 4,4-isopropylidenediphenol, 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 4,4'-dihydroxyphenylsulfone, 4,4 -hexafluoroisopropylidenediphenol, 4,4′,4″-trishydroxyphenylethane, 1,1,1-trishydroxyphenylethane, 4,4′-[1-[4-[1-(4- hydroxyphenyl)-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, phenol compounds such as 2,5-bis(2-hydroxy-5-methylbenzyl)methyl, ethanol, 2- Aliphatic such as propanol, 4-butanol, cyclohexanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 2-methoxyethanol, 2-butoxyethanol, 2-methoxypropanol, 2-butoxypropanol, ethyl lactate, butyl lactate Alcohols can be mentioned.

Examples of compounds containing an amino group 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, and aminocyclohexane.

Furthermore, compounds containing both a hydroxy group and an amino group include, for example, o-aminophenol, m-aminophenol, p-aminophenol, 4-aminoresorcinol, 2,3-diaminophenol, 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-5-hydroxyphenyl)hexafluoropropane and other aminophenols, 2-aminoethanol, 3-aminopropanol, 4-aminocyclohexanol and other alkanolamines can be mentioned.

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

When the first photosensitive resin composition of the present invention is a positive photosensitive resin composition, the content of the compound having a quinonediazide group as component (D-1) is 100 masses of component (A). parts by mass, preferably 5 to 100 parts by mass, more preferably 8 to 50 parts by mass, even more preferably 10 to 40 parts by mass. If the amount is less than 5 parts by mass, the difference in dissolution rate in the developer between the exposed area and the unexposed area of the positive photosensitive resin composition becomes small, and patterning by development may be difficult. On the other hand, if the amount exceeds 100 parts by mass, the 1,2-quinonediazide compound may not be sufficiently decomposed by exposure for a short period of time, resulting in a decrease in sensitivity, or component (D-1) may absorb light, resulting in formation of a cured film. It may reduce transparency.

(D-2) The photo-radical generator is not particularly limited as long as it generates radicals upon exposure. Specific examples include benzophenone, Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-ethylanthraquinone, aromatic ketones such as phenanthrene, benzoin methyl ether, and benzoin ethyl. Ethers, benzoin ethers such as benzoin phenyl ether, benzoins such as methylbenzoin and ethylbenzoin, 2-(o-chlorophenyl)-4,5-phenylimidazole dimer, 2-(o-chlorophenyl)-4,5- Di(m-methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, 2,4,5-triarylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(m-methylphenyl)imidazole dimer, 2-benzyl-2-dimethylamino-1-(4 -morpholinophenyl)-butanone, 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5-(p-cyanostyryl)-1,3,4-oxadiazole , 2-trichloromethyl-5-(p-methoxystyryl)-1,3,4-oxadiazole and other halomethyloxadiazole compounds, 2,4-bis(trichloromethyl)-6-p-methoxystyryl- S-triazine, 2,4-bis(trichloromethyl)-6-(1-p-dimethylaminophenyl-1,3-butadienyl)-S-triazine, 2-trichloromethyl-4-amino-6-p-methoxy Styryl-S-triazine, 2-(naphth-1-yl)-4,6-bis-trichloromethyl-S-triazine, 2-(4-ethoxy-naphth-1-yl)-4,6-bis-trichloro Halomethyl-S-triazine compounds such as methyl-S-triazine, 2-(4-butoxy-naphth-1-yl)-4,6-bis-trichloromethyl-S-triazine, 2,2-dimethoxy-1, 2-diphenylethan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropanone, 1,2-benzyl-2-dimethylamino-1-(4-morpholinophenyl) -butanone-1,1-hydroxy-cyclohexyl-phenyl ketone, benzyl, benzoylbenzoic acid, methyl benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl sulfide, benzyl methyl ketal, dimethylaminobenzoate, p-dimethylaminobenzoic acid isoamyl, 2-n-butoxyethyl-
4-dimethylaminobenzoate, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 1-(4-phenylthiophenyl)-1,2-octanedione-2-(O- benzoyloxime), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), 4-benzoyl-methyldiphenylsulfide, 1- Hydroxy-cyclohexyl-phenyl ketone, 2-benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-1-butanone, 2-(dimethylamino)-2-[(4-methylphenyl ) methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, α-dimethoxy-α-phenylacetophenone, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, diphenyl(2, 4,6-trimethylbenzoyl)phosphine oxide, 2-methyl-1-[4-(methylthio)phenyl]-2-(4-morpholinyl)-1-propanone and the like.
The above photoradical generators are readily available as commercial products, and specific examples thereof include IRGACURE 173, IRGACURE 500, IRGACURE 2959, IRGACURE 754, IRGACURE 907, IRGACURE 369, IRGACURE 1300, IRGACURE 819, IRGACURE 819DW, IRGACURE 1880, IRGACURE 1870, DAROCURE TPO, DAROCURE 4265, IRGACURE 784, IRGACURE OXE01, IRGACURE OXE02, IRGACURE 250 (manufactured by BASF), KAYACURE DETX-S, KAYAC URE CTX, KAYACURE BMS, KAYACURE 2-EAQ (above , manufactured by Nippon Kayaku Co., Ltd.), TAZ-101, TAZ-102, TAZ-103, TAZ-104, TAZ-106, TAZ-107, TAZ-108, TAZ-110, TAZ-113, TAZ-114, TAZ-118, TAZ-122, TAZ-123, TAZ-140, TAZ-204 (manufactured by Midori Chemical Co., Ltd.) and the like.
These photo-radical generators may be used alone, or two or more of them may be used in combination.

When the first photosensitive resin composition of the present invention contains component (D-2), the content is 0.1 to 30 parts by mass with respect to 100 parts by mass of component (A). is preferred, more preferably 0.5 to 20 parts by mass, and particularly preferably 1 to 15 parts by mass. If this ratio is too small, the exposed portion may be insufficiently cured, and the pattern may not be formed, or even if it is formed, the film may be unreliable. On the other hand, if this ratio is excessively high, the transmittance of the coating film may be lowered, or development failure may occur in the unexposed areas.

The photoacid generator (D-3) is not particularly limited as long as it is a compound that photodecomposes upon exposure to ultraviolet rays to generate an acid. Acids generated when the photoacid generator is photolyzed include, for example, hydrochloric acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentanesulfonic acid, octanesulfonic acid, benzenesulfonic acid, p- toluenesulfonic acid, camphorsulfonic acid, trifluoromethanesulfonic acid, p-phenolsulfonic acid, 2-naphthalenesulfonic acid, mesitylenesulfonic acid, p-xylene-2-sulfonic acid, m-xylene-2-sulfonic acid, 4-ethylbenzene Sulfonic acid, 1H,1H,2H,2H-perfluorooctanesulfonic acid, perfluoro(2-ethoxyethane)sulfonic acid, pentafluoroethanesulfonic acid, nonafluorobutane-1-sulfonic acid, sulfones such as dodecylbenzenesulfonic acid Acids or their hydrates and salts are mentioned.

Examples of photoacid generators include diazomethane compounds, onium salt compounds, sulfonimide compounds, disulfone compounds, sulfonic acid derivative compounds, nitrobenzyl compounds, benzoin tosylate compounds, iron arene complexes, halogen-containing triazine compounds, and acetophenone derivative compounds. , and cyano group-containing oxime sulfonate compounds.
Any conventionally known or conventionally used photoacid generator can be applied in the present invention without particular limitation. In the present invention, the component (D) photoacid generator may be used alone or in combination of two or more. Specific examples include compounds represented by the following formulas [PAG-1] to [PAG-41].

When the first photosensitive resin composition of the present embodiment contains component (D-3), the content is preferably 0.01 parts by mass to 20 parts by mass with respect to 100 parts by mass of component (A). parts, more preferably 0.1 to 10 parts by mass, still more preferably 0.5 to 8 parts by mass. By setting the content of component (D-3) to 0.01 part by mass or more, sufficient thermosetting and solvent resistance can be imparted. However, if the amount is more than 20 parts by mass, the unexposed area may be poorly developed, or the storage stability of the composition may be lowered.

<(E) component>
Component (E) is a cross-linking agent, which is introduced into the composition when the first photosensitive resin composition of the present invention satisfies the requirement (Z1). More specifically, it is a compound having a structure capable of forming a crosslinked structure by thermal reaction with the heat-reactive site (eg, carboxyl group and/or phenolic hydroxy group) of component (A). Specific examples are given below, but are not limited to these. The thermal cross-linking agent is selected from, for example, (E1) a cross-linking compound having two or more substituents selected from alkoxymethyl groups and hydroxymethyl groups and (E2) a cross-linking compound represented by the following formula (1). is preferred. 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 alkoxymethyl groups and hydroxymethyl groups, which is the component (E1), is exposed to a high temperature during thermosetting, the crosslinking reaction proceeds through a dehydration condensation reaction. . Such compounds include, for example, compounds such as alkoxymethylated glycoluril, alkoxymethylated benzoguanamine, and alkoxymethylated melamine, and phenoplastic compounds.

Specific examples of alkoxymethylated glycoluril include 1,3,4,6-tetrakis(methoxymethyl)glycoluril, 1,3,4,6-tetrakis(butoxymethyl)glycoluril, 1,3,4 ,6-tetrakis(hydroxymethyl)glycoluril, 1,3-bis(hydroxymethyl)urea, 1,1,3,3-tetrakis(butoxymethyl)urea, 1,1,3,3-tetrakis(methoxymethyl) urea, 1,3-bis(hydroxymethyl)-4,5-dihydroxy-2-imidazolinone, 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazolinone and the like. Commercially available products include compounds such as glycoluril compounds manufactured by Mitsui Cytec Co., Ltd. (trade name: Cymel (registered trademark) 1170, Powderlink (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), DIC Corporation urea / formaldehyde resin (high condensation type, trade name: Beccamin ( registered trademarks) J-300S, P-955, N) and the like.

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

Specific examples of alkoxymethylated melamine include hexamethoxymethylmelamine. As commercially available products, Mitsui Cytec Co., Ltd. methoxymethyl type melamine compounds (trade names: Cymel (registered trademark) 300, Cymel 301, Cymel 303, and 350), butoxymethyl type melamine compounds (trade name: Mycoat (registered trademark) ) 506, 508), Sanwa Chemical methoxymethyl type melamine compounds (trade names: Nikalac (registered trademark) MW-30, MW-22, MW-11, MW-100LM, MS-001, MX-002, MX-730, MX-750, MX-035), butoxymethyl-type melamine compounds (trade names: Nikalac (registered trademark) MX-45, MX-410, MX-302), etc. mentioned.

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

Specific examples of phenoplast compounds include 2,6-bis(hydroxymethyl)phenol, 2,6-bis(hydroxymethyl)cresol, 2,6-bis(hydroxymethyl)-4-methoxyphenol, 3 , 3′,5,5′-tetrakis(hydroxymethyl)biphenyl-4,4′-diol, 3,3′-methylenebis(2-hydroxy-5-methylbenzenemethanol), 4,4′-(1-methyl ethylidene)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 -methylbenzenemethanol), 4,4′-(1-methylethylidene)bis[2-methyl-6-methoxymethylphenol], 4,4′-methylenebis[2-methyl-6-methoxymethylphenol], 4, 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 commercial product, and specific examples include 26DMPC, 46DMOC, DM-BIPC-F, DM-BIOC-F, TM-BIP-A, BISA-F, BI25X-DF, BI25X-TPA ( The above, manufactured by Asahi Organic Chemicals Industry Co., Ltd.) and the like can be mentioned.

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

Examples of such polymers include poly(N-butoxymethylacrylamide), copolymers of N-butoxymethylacrylamide and styrene, copolymers of N-hydroxymethylmethacrylamide and methylmethacrylate, N-ethoxymethyl Copolymers of methacrylamide and benzyl methacrylate, copolymers of N-butoxymethylacrylamide, benzyl methacrylate and 2-hydroxypropyl methacrylate, and the like are included. Such polymers have a weight average molecular weight of 1,000 to 50,000, preferably 1,500 to 20,000, more preferably 2,000 to 10,000.

（式中、ｋは２乃至１０の整数、ｍは０乃至４の整数を示し、Ｒ^１１はｋ価の有機基を表す） Moreover, the first photosensitive resin composition of the present invention can contain a crosslinkable compound represented by the following formula (1) as the (E2) component.

(Wherein, k is an integer of 2 to 10, m is an integer of 0 to 4, and R ¹¹ represents a k-valent organic group)

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

Commercially available products include Epolead GT-401, Epolead GT-403, Epolead GT-301, Epolead GT-302, Celoxide 2021, Celoxide 3000 (manufactured by Daicel Co., Ltd.), and Denacol EX-, an alicyclic epoxy resin. 252 (manufactured by Nagase ChemteX Corporation), CY175, CY177, CY179 (manufactured by Huntsman Corporation), Araldite CY-182, CY-192, CY-184 (manufactured by Huntsman Corporation) ), Epiclon 200, Epiclon 400 (these are the trade names of DIC Corporation), Epicort 871 and Epicort 872 (these are the trade names of Mitsubishi Chemical Corporation), ED-5661, ED-5662 (these are Celanese Coating Co., Ltd. product name), etc. can be mentioned. Moreover, these crosslinkable compounds can be used individually or in combination of 2 or more types.

Among them, compounds represented by formulas E2-1 and E2-2, which have a cyclohexene oxide structure from the viewpoint of heat resistance, solvent resistance, process resistance such as long-term baking resistance, and transparency, and Epolead GT-401, GT-403, GT-301, GT-302, Celoxide 2021 and Celoxide 3000 are preferred.

In addition, as component E, components (E1) and (E2) are heat-reactive sites (e.g., carboxyl groups and/or phenolic hydroxy groups) of component (A) other than those shown as component (E2). can also be used. Specifically, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexane. diol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N,N,N',N', -tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, and N,N,N',N',-tetraglycidyl-4,4'-diaminodiphenylmethane, etc. Epoxy compound, VESTANAT B1358/100, VESTAGON BF 1540 (above, isocyanurate-type modified polyisocyanate, manufactured by Degussa Japan Co., Ltd.), Takenate (registered trademark) B-882N, Takenate B-7075 (above, isocyanurate-type modified Examples include isocyanate compounds such as polyisocyanate and Mitsui Chemicals, Inc.).

Also, as component E, a polymer having two or more structures capable of forming a cross-linked structure by thermal reaction with the heat-reactive sites (e.g., carboxyl groups and/or phenolic hydroxy groups) of component (A) should be used. can be done. Specifically, for example, polymers produced using compounds having an epoxy group such as glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3-methacryloxypropyltrimethoxy Polymer produced using a compound having an alkoxysilyl group such as silane, 2-isocyanatoethyl methacrylate (Karenzu MOI [registered trademark], manufactured by Showa Denko Co., Ltd.), 2-isocyanatoethyl acrylate (Karenzu AOI [ registered trademark], manufactured by Showa Denko Co., Ltd.), or 2-(0-[1′-methylpropylideneamino]carboxyamino)ethyl methacrylate (KarenzuMOI-BM [registered trademark], Showa Denko Co., Ltd.), 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate (Karenzu MOI-BP [registered trademark], Showa Denko Co., Ltd.) and other compounds having a blocked isocyanate group. Polymers made using These compounds may be used singly or in combination to produce a polymer, or may be combined with other compounds to produce a polymer.

(A) When the component has at least one group that reacts with a group selected from the group consisting of a hydroxyl group, a carboxyl group, an amido group, and an amino group, a hydroxyl group, a carboxyl group, an amido group, 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 first photosensitive resin composition of the present invention, the content is 1 part by mass to 50 parts by mass, preferably 1 part by mass with respect to 100 parts by mass of the component (A). It is from 1 to 40 parts by mass, more preferably from 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 the effect of improving heat resistance after pattern formation, solvent resistance, resistance to long-term baking, etc. may not be obtained. On the other hand, if it exceeds 50 parts by mass, uncrosslinked crosslinkable compounds are present, and the heat resistance after pattern formation, solvent resistance, resistance to long-term baking, etc. are lowered, and the photosensitive resin composition is also deteriorated. storage stability may deteriorate.

<(F) Component>
Component (F) is a compound having two or more ethylenically polymerizable groups. The term "compound having two or more ethylenically polymerizable groups" as used herein means a compound having two or more polymerizable groups in one molecule and having those polymerizable groups at the ends of the molecule. , the polymerizable group means at least one polymerizable group selected from the group consisting of an acrylate group, a methacrylate group, a vinyl group and an allyl group.
The compound having two or more ethylenic polymerizable groups, which is the component (F), is compatible with each component in the solution of the negative photosensitive resin composition in the first photosensitive resin composition of the present invention. A compound having a molecular weight (weight-average molecular weight when the compound is a polymer) of 1,000 or less is preferred from the viewpoint of good performance and no influence on developability.

Specific examples of such compounds include dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, pentaerythritol triacrylate, and pentaerythritol triacrylate. Erythritol trimethacrylate, pentaerythritol diacrylate, pentaerythritol dimethacrylate, tetramethylolpropane tetraacrylate, tetramethylolpropane tetramethacrylate, tetramethylolmethanetetraacrylate, tetramethylolmethanetetramethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, 1,3,5-triacryloyl hexahydro-S-triazine, 1,3,5-trimethacryloyl hexahydro-S-triazine, tris(hydroxyethyl acryloyl) isocyanurate, tris(hydroxyethyl methacryloyl) isocyanurate, triacryloyl formal, trimethacryloyl formal, 1,6-hexanediol acrylate, 1,6-hexanediol methacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, ethanediol diacrylate, ethanediol dimethacrylate, 2-hydroxypropanediol diol Acrylates, 2-hydroxypropanediol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, isopropylene glycol diacrylate, isopropylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, N,N'-bis(acryloyl ) cysteine, N,N'-bis(methacryloyl)cysteine, thiodiglycol diacrylate, thiodiglycol dimethacrylate, bisphenol A diacrylate, bisphenol A dimethacrylate, bisphenol F diacrylate, bisphenol F dimethacrylate, bisphenol S diacrylate , bisphenol S dimethacrylate, bisphenoxyethanol fluorenediacrylate, bisphenoxyethanolfluorenedimethacrylate, diallyl ether bisphenol A, o-diallyl bisphenol A, diallyl maleate, triallyl trimellitate and the like.

The above polyfunctional acrylate compounds are readily available as commercial products, and specific examples include KYARAD T-1420, DPHA, DPHA-2C, D-310, D-330, DPCA-20, DPCA-30, DPCA-60, DPCA-120, DN-0075, DN-2475, R-526, NPGDA, PEG400DA, MANDA, R-167, HX -220, HX620, R-551, R-712, R-604, R-684, GPO-303, TMPTA, THE-330, TPA-320, TPA-330, PET-30, RP-1040 (manufactured by Nippon Kayaku Co., Ltd.), Aronix M-210, M-240, M-6200, M-309, M-400, M-402, M-405, M-450, M-7100, M-8030, M-8060, M-1310, M-1600, M-1960, M-8100, M-8530, M-8560, M-9050 (manufactured by Toagosei Co., Ltd.), Viscoat 295, 300, 360, GPT, 3PA, 400, 260, 312, 335HP (Osaka Organic Chemical Industry Co., Ltd.), A-9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A-TMM-3LM-N, A-TMPT, AD -TMP, ATM-35E, A-TMMT, A-9550, A-DPH, TMPT, 9PG, 701, 1206PE, NPG, NOD-N, HD-N, DOD-N, DCP, BPE-1300N, BPE-900 , BPE-200, BPE-100, BPE-80N, 23G, 14G, 9G, 4G, 3G, 2G, 1G (all manufactured by Shin-Nakamura Chemical Co., Ltd.).
These compounds having two or more ethylenic polymerizable groups can be used singly or in combination of two or more.

The content of component (F) in the first photosensitive resin composition of the present invention is preferably 5 parts by mass to 200 parts by mass, more preferably 100 parts by mass of component (A). is 10 to 150 parts by mass, particularly preferably 50 to 150 parts by mass. If this ratio is too small, the exposed portion will be insufficiently cured, and there is a possibility that the pattern cannot be formed, or even if it is formed, the film will be unreliable. If this ratio is too high, tackiness may occur in the pre-baked coating film, or the unexposed portion may become poorly dissolved during development.

<(G) Component>
The (G) component used in the first photosensitive resin composition of the present invention is a compound having two or more functional groups that form a covalent bond with an acid. Examples of functional groups that form covalent bonds with acids include epoxy groups, alkoxymethyl groups, and hydroxymethyl groups.

Examples of compounds having two or more epoxy groups include tris(2,3-epoxypropyl)isocyanurate, 1,4-butanediol diglycidyl ether, 1,2-epoxy-4-(epoxyethyl)cyclohexane, and glycerol. Triglycidyl ether, diethylene glycol diglycidyl ether, 2,6-diglycidylphenyl glycidyl ether, 1,1,3-tris[p-(2,3-epoxypropoxy)phenyl]propane, diglycidyl 1,2-cyclohexanedicarboxylate esters, 4,4′-methylenebis(N,N-diglycidylaniline), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, trimethylolethane triglycidyl ether and bisphenol-A-diglycidyl ether, and pentaerythritol polyglycidyl ether.

As the compound having two or more epoxy groups, a commercially available compound may be used because it is easily available. Specific examples (trade names) are listed below, but are not limited to: Epoxy resins having an amino group such as YH-434 and YH434L (manufactured by Shin Nikka Epoxy Mfg. Co., Ltd.); Epolead GT- epoxy resins having a cyclohexene oxide structure such as 401, GT-403, GT-301, GT-302, Celoxide 2021, Celoxide 3000 (manufactured by Daicel Corporation); Epicoat 1001, 1002, 1003, 1004 , 1007, 1009, 1010, 828 (manufactured by Yuka Shell Epoxy Co., Ltd. (currently Mitsubishi Chemical Co., Ltd.)) and other bisphenol A type epoxy resins; Bisphenol F type epoxy resins such as (currently manufactured by Mitsubishi Chemical Corporation); , Nippon Kayaku Co., Ltd.) and other phenol novolac epoxy resins; ), cresol novolac type epoxy resins such as Epicoat 180S75 (manufactured by Yuka Shell Epoxy Co., Ltd. (currently Mitsubishi Chemical Corporation)); Araldite CY-182, Araldite CY-192, and CY-184 (above, Huntsman
Corporation), Epiclon 200, Epiclon 400 (manufactured by Dainippon Ink and Chemicals Co., Ltd. (currently DIC Corporation)), Epicort 871, Epicort 872 (manufactured by Yuka Shell Epoxy Co., Ltd. (currently Mitsubishi Chemical Co., Ltd.) Ltd.), ED-5661, ED-5662 (manufactured by Celanese Coating Co., Ltd.); 622, EX-411, EX-512, EX-522, EX-421, EX-313, EX-314, EX-321 (manufactured by Nagase ChemteX Corporation), etc. glycidyl ether and the like.

A polymer having an epoxy group can also be used as the compound having two or more epoxy groups.
The epoxy group-containing polymer can be produced, for example, by addition polymerization using an epoxy group-containing addition polymerizable monomer. Examples thereof include addition polymerization polymers such as polyglycidyl acrylate, copolymers of glycidyl methacrylate and ethyl methacrylate, copolymers of glycidyl methacrylate, styrene and 2-hydroxyethyl methacrylate, and condensation polymerization polymers such as epoxy novolak. .

Alternatively, the epoxy group-containing polymer can be produced by reacting a hydroxyl group-containing polymer with an epoxy group-containing compound such as epichlorohydrin or glycidyl tosylate.

The weight average molecular weight of such polymers is, for example, 300 to 20,000.

These compounds having two or more epoxy groups can be used alone or in combination of two or more.

Compounds having two or more substituents selected from alkoxymethyl groups and hydroxymethyl groups include, for example, compounds such as alkoxymethylated glycoluril, alkoxymethylated benzoguanamine, and alkoxymethylated melamine, and phenoplast compounds. .

Specific examples of alkoxymethylated glycoluril are as described in paragraph [0108] above.

Specific examples of the alkoxymethylated benzoguanamine are as described in paragraph [0109] above.

Specific examples of the alkoxymethylated melamine are as described in paragraph [0110] above.

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

Specific examples of the phenoplast-based compound are as described in paragraph [0112] above.

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

Examples of such polymers include poly(N-butoxymethylacrylamide), copolymers of N-butoxymethylacrylamide and styrene, copolymers of N-hydroxymethylmethacrylamide and methylmethacrylate, N-ethoxymethyl Copolymers of methacrylamide and benzyl methacrylate, copolymers of N-butoxymethylacrylamide, benzyl methacrylate and 2-hydroxypropyl methacrylate, and the like are included. Such polymers have a weight average molecular weight of 1,000 to 50,000, preferably 1,500 to 20,000, more preferably 2,000 to 10,000.

When the first photosensitive resin composition of the present invention contains a compound having two or more functional groups that form a covalent bond with an acid as component (G), the content is based on 100 parts by mass of component (A). 5 parts by mass to 200 parts by mass, more preferably 50 parts by mass to 150 parts by mass. If this ratio is too small, the photocurability of the negative photosensitive resin composition may be lowered, while if it is too large, the developability of the unexposed area is lowered, resulting in residual film or residue. It may be the cause.

<Other additives>
Furthermore, the first photosensitive resin composition used in the present invention may optionally contain leveling agents, surfactants, rheology modifiers, pigments, dyes, storage stabilizers, as long as the effects of the present invention are not impaired. Antifoaming agents, adhesion promoters, or dissolution promoters such as polyhydric phenols and polyhydric carboxylic acids can be contained.
As the surfactant, a fluoropolymer fluorosurfactant is preferably used. Examples of such fluorosurfactants include Megafac (registered trademark) F-251, F-281, F-430, F-444, R-30, R-40, and F-553. , F-554, F-555, F-556, F-557, F-558 (manufactured by DIC Corporation), Surflon (registered trademark) S-242, S-243, S-385, S-386
, S-420 and S-611 (manufactured by ACG Seimi Chemical Co., Ltd.). These fluorosurfactants may be used alone or in combination of two or more.

<Resist film forming process>
After forming the underlayer film 12 as described above, the second photosensitive resin composition is applied onto the underlayer film 12 and prebaked to form a resist film 13 (FIG. 1). Generally, the second photosensitive resin composition is applied to the entire surface of the lower layer film 12 to form the resist film 13 .
Details of each component of the resist film will be described below.

<(a) component>
The component (a) of the present invention is a resin having an alkali-soluble group. Alkali-soluble groups include, for example, phenolic hydroxy groups, carboxyl groups, acid anhydride groups, imide groups, sulfonyl groups, phosphoric acid groups, boronic acid groups and active methylene groups and active methine groups.

The active methylene group means a methylene group ( _--CH.sub.2-- ) having a carbonyl group at an adjacent position and having reactivity with a nucleophilic reagent. In the present invention, the active methine group refers to the active methylene group having a structure in which one hydrogen atom of the methylene group is substituted with an alkyl group and having reactivity with a nucleophilic reagent.

（式（ａ１）中、Ｒはアルキル基、アルコキシ基又はフェニル基を表し、破線は結合手を表す。） Among active methylene groups and active methine groups, active methylene groups are preferred, and active methylene groups represented by the following formula (a1) are more preferred.

(In formula (a1), R represents an alkyl group, an alkoxy group, or a phenyl group, and the dashed line represents a bond.)

In the above formula (a1), the alkyl group represented by R includes, for example, an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 5 carbon atoms.
Examples of such alkyl groups include methyl, ethyl, n-propyl and i-propyl groups.
Among them, a methyl group, an ethyl group, an n-propyl group and the like are preferable.

In the above formula (a1), the alkoxy group represented by R includes, for example, an alkoxy group having 1 to 20 carbon atoms, preferably an alkoxy group having 1 to 5 carbon atoms.
Examples of such alkoxy groups include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy and t-butoxy groups.
Among them, methoxy group, ethoxy group, n-propoxy group and the like are preferable.

Examples of the group represented by formula (a1) include the following structures. In the structural formulas, dashed lines represent bonds.

Among the above alkali-soluble groups, an alkali-soluble resin having at least one organic group selected from the group consisting of a phenolic hydroxyl group and a carboxyl group and having a number average molecular weight of 2,000 to 50,000. Preferably.

The alkali-soluble resin of component (a) may be any alkali-soluble resin having such a structure, and there are no particular restrictions on the skeleton of the polymer main chain and the types of side chains that constitute the resin.

However, the alkali-soluble resin of component (a) has a number average molecular weight within the range of 2,000 to 50,000. If the number average molecular weight is too large, exceeding 50,000, development residues are likely to occur, and the sensitivity is greatly reduced. At that time, a considerable amount of film loss occurs in the exposed area, which may result in insufficient curing.

Examples of the alkali-soluble resin (a) include acrylic resins, polyhydroxystyrene resins, polyimide precursors, and polyimides.

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

That is, the above-mentioned specific copolymer is selected from the group of monomers exhibiting alkali solubility, that is, monomers having at least one selected from the group consisting of phenolic hydroxy groups and carboxyl groups, and monomers copolymerizable with these monomers. It is a copolymer formed with at least one selected monomer as an essential structural unit, and has a number average molecular weight of 2,000 to 50,000. A number average molecular weight greater than 50,000 may result in residue.

The "monomer having at least one selected from the group consisting of a phenolic hydroxy group and a carboxyl group" includes monomers having a phenolic hydroxy group and monomers having a carboxyl group. These monomers are not limited to having one phenolic hydroxy group or carboxyl group, and may have a plurality of phenolic hydroxy groups or carboxyl groups.

Specific examples of the above monomers are listed below, but are not limited thereto.
Examples of monomers having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, mono-(2-(acryloyloxy)ethyl) phthalate, mono-(2-(methacryloyloxy)ethyl) phthalate, N-(carboxyphenyl ) maleimide, N-
(Carboxyphenyl) methacrylamide, N-(carboxyphenyl) acrylamide and the like.

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

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 component (a) alkali-soluble resin is Of the monomers, it is preferably 5 mol % to 90 mol %, more preferably 10 mol % to 60 mol %, most preferably 10 mol % to 30 mol %. If the unsaturated carboxylic acid derivative is less than 5% by weight, the alkali solubility of the polymer is insufficient.

The alkali-soluble resin, which is the component (a) of the present invention, is obtained by copolymerizing a monomer having a hydroxyalkyl group and a polymerizable unsaturated group in order to further stabilize the pattern shape after curing. is preferred.

Examples of monomers having a hydroxyalkyl group and a polymerizable unsaturated group include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2,3-dihydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 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 component (a) alkali-soluble resin is preferably 5% by mass to 60% by mass, more preferably 10% by mass to 50% by mass, most preferably Preferred is 20% to 40% by mass. If the amount of the monomer having a hydroxyalkyl group and a polymerizable unsaturated group is less than 5% by mass, the effect of stabilizing the pattern shape of the copolymer may not be obtained. If the amount is 60% by mass or more, the alkali-soluble groups of component (a) may be insufficient, resulting in deterioration of properties such as developability.

The alkali-soluble resin, which is the component (a) of the present invention, is preferably copolymerized with an N-substituted maleimide compound in order to raise 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 preferred, and from the viewpoints of developability, transparency and heat resistance, those having an alicyclic skeleton are more preferred, and cyclohexylmaleimide is most preferred.

The ratio of the N-substituted maleimide in the production of the component (a) alkali-soluble resin is preferably 5% to 60% by mass, more preferably 10% to 50% by mass, and most preferably 20% to 40% by mass. %. If the N-substituted maleimide content is less than 5% by mass, the copolymer may have a low Tg and poor heat resistance. If it is 60% by mass or more, the transparency may deteriorate.

When the second photosensitive resin composition of the present invention satisfies the requirement (z2), the alkali-soluble resin of component (a) used in the present invention further has a self-crosslinking group, or has a hydroxy group, a carboxyl 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 groups, amido groups and amino groups.

Examples of the self-crosslinkable groups include N-alkoxymethyl groups, N-hydroxymethyl groups, alkoxysilyl groups, epoxy groups, oxetane groups, vinyl groups and blocked isocyanate groups.

Examples of the crosslinkable groups include N-alkoxymethyl groups, N-hydroxymethyl groups, alkoxysilyl groups, epoxy groups, vinyl groups, blocked isocyanate groups and the like.

When the self-crosslinking group or crosslinkable group is contained in the component (a) alkali-soluble resin, the content thereof is 0.1 to 0.9 per repeating unit in the component (a) resin. , and more preferably 0.1 to 0.8 from the viewpoint of developability and solvent resistance.

The alkali-soluble resin of component (a) further contains self-crosslinking groups such as N-alkoxymethyl groups, N-hydroxymethyl groups, alkoxysilyl groups, epoxy groups, oxetane groups, vinyl groups and blocked isocyanate groups, and N-alkoxymethyl groups. group, an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, a vinyl group, a repeating unit having at least one selected from a crosslinkable group such as a blocked isocyanate group, for example, having radical polymerizability, epoxy crosslinkable groups such as groups, oxetane groups, vinyl groups and blocked isocyanate groups; and self-crosslinkable groups such as N-alkoxymethyl groups, N-hydroxymethyl groups and alkoxysilyl groups. Copolymerization may be carried out.

Radically polymerizable unsaturated compounds having an N-alkoxymethyl group include N-butoxymethylacrylamide, N-isobutoxymethylacrylamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, and N-methylolacrylamide. etc.

Examples of monomers having radical polymerizability and having an N-hydroxymethyl group include N-hydroxymethylacrylamide and N-hydroxymethylmethacrylamide.

Examples of monomers having radical polymerizability and having an alkoxysilyl group include 3-acryloyloxytrimethoxysilane, 3-acryloyloxytriethoxysilane, 3-methacryloyloxytrimethoxysilane, 3-methacryloyloxytriethoxysilane, and the like. mentioned.

Examples of the radically polymerizable unsaturated compound having an epoxy group include glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethylacrylate, glycidyl α-n-propylacrylate, and α-n-butyl acrylate. glycidyl, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl methacrylate, α-ethyl acrylate-6, 7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3,4-epoxycyclohexyl methacrylate and the like. Among these, glycidyl methacrylate, 6,7-epoxyheptyl methacrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3,4-epoxycyclohexyl methacrylate, etc. It is preferably used. These are used singly or in combination.

Examples of unsaturated compounds having radical polymerizability and having an oxetane group include (meth)acrylic acid esters having an oxetane group. Among such monomers, 3-(methacryloyloxymethyl)oxetane, 3-(acryloyloxymethyl)oxetane, 3-(methacryloyloxymethyl)-3-ethyl-oxetane, 3-(acryloyloxymethyl)- 3-ethyl-oxetane, 3-(methacryloyloxymethyl)-2-trifluoromethyloxetane, 3-(acryloyloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloyloxymethyl)-2-phenyl-oxetane, 3-(acryloyloxymethyl)-2-phenyl-oxetane, 2-(methacryloyloxymethyl)oxetane, 2-(acryloyloxymethyl)oxetane, 2-(methacryloyloxymethyl)-4-trifluoromethyloxetane, 2-( Acryloyloxymethyl)-4-trifluoromethyloxetane is preferred, and 3-(methacryloyloxymethyl)-3-ethyl-oxetane, 3-(acryloyloxymethyl)-3-ethyl-oxetane and the like are preferably used.

Monomers having radical polymerizability and having a vinyl group include 2-(2-vinyloxyethoxy)ethyl acrylate and 2-(2-vinyloxyethoxy)ethyl methacrylate.

Examples of radically polymerizable monomers having a blocked isocyanate group include 2-(0-(1′-methylpropylideneamino)carboxyamino)ethyl methacrylate and 2-(3,5-dimethylpyrazolyl) methacrylate. carbonylamino)ethyl and the like.

When the second photosensitive resin composition of the present invention satisfies (z1), it has radical polymerizability and includes an N-alkoxymethyl group, N-hydroxymethyl group, alkoxysilyl group, epoxy group, oxetane group, vinyl At least one group selected from self-crosslinkable groups such as groups and blocked isocyanate groups, and crosslinkable groups such as N-alkoxymethyl groups, N-hydroxymethyl groups, alkoxysilyl groups, epoxy groups, vinyl groups, and blocked isocyanate groups Preferably 10% by mass to 70% by mass, particularly preferably 20% by mass to It contains 60% by mass. If the amount of this structural unit is less than 10% by mass, the heat resistance and surface hardness of the resulting cured film tend to decrease. It tends to be less stable.

In the present invention, the acrylic polymer of component (a) may be a copolymer in which monomers other than the above monomers (hereinafter referred to as other monomers) are also used as structural units. Other monomers may specifically be copolymerizable with at least one selected from the group consisting of the above-mentioned monomers having a carboxyl group and monomers having a phenolic hydroxyl group. It is not particularly limited as long as it does not damage it. Specific examples of such monomers include acrylic acid ester compounds, methacrylic acid ester compounds, maleimide, acrylamide compounds, acrylonitrile, styrene compounds and vinyl compounds.
Specific examples of the other monomer are listed below, but are not limited thereto.

Examples of the acrylic ester compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, glycidyl acrylate, 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 2-(acryloyloxy)ethyl ester, poly(ethylene glycol) ethyl ether acrylate, and the like.

Examples of the methacrylate compounds 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, diethylene glycol monomethacrylate, caprolactone 2-(methacryloyloxy)ethyl ester, poly(ethylene glycol) ethyl ether methacrylate and the like.

Examples of the acrylamide compounds include N-methylacrylamide, N-methylmethacrylamide, N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, N-butoxy Methyl acrylamide, N-butoxymethyl methacrylamide and the like.

Examples of the vinyl compound include methyl vinyl ether, benzyl vinyl ether, cyclohexyl vinyl ether, vinylnaphthalene, vinylanthracene, vinylcarbazole, allyl glycidyl ether, 3-ethenyl-7-oxabicyclo[4.1.0]heptane, 1,2 -epoxy-5-hexene and 1,7-octadiene monoepoxide.

Examples of the styrene compound include styrene having no hydroxyl group, such as styrene, α-methylstyrene, chlorostyrene, and bromostyrene.

In the production of the alkali-soluble resin as component (a), the ratio of the other monomers is preferably 80% by mass or less, more preferably 50% by mass or less, and even more preferably 20% by mass or less. If the content exceeds 80% by mass, the amount of essential components is relatively reduced, making it difficult to sufficiently obtain the effects of the present invention.

The method for obtaining the alkali-soluble resin, which is the component (a) used in the present invention, is not particularly limited. a monomer having at least one selected from the group consisting of groups, a monomer having a hydroxyalkyl group, optionally an N-alkoxymethyl group, an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, an oxetane group, a vinyl group and a blocked isocyanate A monomer having at least one group selected from self-crosslinking groups such as groups and crosslinkable groups such as N-alkoxymethyl groups, N-hydroxymethyl groups, alkoxysilyl groups, epoxy groups, vinyl groups, and blocked isocyanate groups, It can be obtained by carrying out a polymerization reaction at a temperature of 50°C to 110°C in a solvent in which other copolymerizable monomers, if desired, and a polymerization initiator, etc. are allowed to coexist. At that time, the solvent used is not particularly limited as long as it dissolves the monomers constituting the alkali-soluble resin and the acrylic polymer having a specific functional group. Specific examples include the solvents described in component (c), which will be described later.

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

In addition, the solution of the specific copolymer obtained as described above is added to diethyl ether, water, or the like under stirring to reprecipitate, and after filtering and washing the generated precipitate, 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 unreacted monomers coexisting with the specific copolymer can be removed, and as a result, a purified powder of the specific copolymer can be obtained. If the purification cannot be sufficiently performed in 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 above-mentioned specific copolymer may be used as it is, or the powder may be redissolved in the component (c), which will be described later, for example, and used in the form of a solution.

As the alkali-soluble resin of component (a), polyimide precursors such as polyamic acid, polyamic acid ester, and partially imidized polyamic acid, and polyimides such as carboxylic acid group-containing polyimides can be used. As long as it is soluble, it can be used without particular limitation on its type.

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

The (i) tetracarboxylic dianhydride compound is not particularly limited, and specific examples include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3' ,4,4′-benzophenonetetracarboxylic dianhydride, 3,3′,4,4′-diphenyl ether tetracarboxylic dianhydride, 3,3′,4,4′-diphenylsulfonetetracarboxylic dianhydride aromatic tetracarboxylic acids such as 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 Carboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides such as 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic dianhydride, 1,2,3, Aliphatic tetracarboxylic dianhydrides such as 4-butanetetracarboxylic dianhydride may be mentioned.
These may be used singly or in combination of two or more.

The diamine compound (j) is also not particularly limited, and examples thereof include 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, and 4,6-diamino-1. , 3-benzenedicarboxylic 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-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)methane, 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)hexafluoro Propane, 2,2-bis(4-amino-3-hydroxyphenyl)hexafluoropropane, 2,2-bis(4-amino-3,5-dihydroxyphenyl)hexafluoropropane, 4,4'-diamino-3 ,3′-dihydroxybiphenyl, 4,4′-diamino-3,3′-dihydroxy-5,5′-dimethylbiphenyl, 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]sulfone, bis[4-(3-amino-4-hydroxyphenoxy) ) Phenyl]propane, diamine compounds having a phenolic hydroxy group such as 2,2-bis[4-(3-amino-4-hydroxyphenoxy)phenyl]hexafluoropropane, 1,3-diamino-4-mercaptobenzene, 1 , 3-diamino-5-mercaptobenzene, 1,4-diamino-2-mercaptobenzene, bis(4-amino-3-mercaptophenyl)ether, 2,2-bis(3-amino-4-mercaptophenyl)hexa Diamine compounds having a thiophenol group such as fluoropropane, 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, 4,4'-diamino-3,3'-dimethylbiphenyl-6,6'-disulfonic acid, etc. A diamine compound having a sulfonic acid group can be mentioned. 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- tolidine, m-tolidine, 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 -toluyl)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, etc. compounds can be mentioned.
These may be used singly or in combination of two or more.

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

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

In the production of polyamic acid, the reaction temperature for the reaction between the diamine compound and the tetracarboxylic dianhydride compound can be selected from -20°C to 150°C, preferably from -5°C to 100°C. In order to obtain polyamic acid having a high molecular weight, a reaction temperature of 5° C. to 40° C. and a reaction time of 1 hour 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 a reaction temperature of 40° C. to 90° C. and a reaction time of 10 hours or longer.
When the terminal amino group is protected with an acid anhydride, the reaction temperature can be selected from -20°C to 150°C, preferably from -5°C 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 that time include N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, N-vinylpyrrolidone, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, Hexamethylsulfoxide, 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 include methyl isobutyl ketone, 2-heptanone, and the like. These may be used singly or in combination. Further, even a solvent that does not dissolve the polyamic acid may be mixed with the above solvent and used as long as the polyamic acid produced by the polymerization reaction does not precipitate out.

The solution containing polyamic acid thus obtained can be used as it is for the preparation of a photosensitive resin composition. Alternatively, the polyamic acid can be precipitated and isolated in a poor solvent such as water, methanol, ethanol, etc., and then recovered and used.

Any polyimide can also be used as the component (a). The polyimide used in the present invention is obtained by chemically or thermally imidizing 50% or more of a polyimide precursor such as polyamic acid.

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

Such a polyimide can be obtained by synthesizing a polyimide precursor such as the polyamic acid described above, followed by 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. As a thermal imidization method, a method of heating a polyimide precursor solution at a temperature of 180° C. to 250° C. while dehydrating it is generally used.

Phenol novolac resin can also be used as the alkali-soluble resin of component (a).

Polyester polycarboxylic acid can also be used as the alkali-soluble resin of component (a). A polyester polycarboxylic acid can be obtained from an acid dianhydride and a diol by the method described in WO2009/051186.
Examples of acid dianhydrides include the above (i) tetracarboxylic dianhydrides.
Diols include aromatic diols such as bisphenol A, bisphenol F, 4,4′-dihydroxybiphenyl, benzene-1,3-dimethanol and benzene-1,4-dimethanol, hydrogenated bisphenol A and hydrogenated bisphenol F. , 1,4-cyclohexanediol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol and other alicyclic diols, and ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol and other aliphatic diols such as

In the present invention, the component (a) alkali-soluble resin may be a mixture of a plurality of alkali-soluble resins.

<(b) component>
The fine particles of component (b) used in the present invention are fine particles of colorants such as pigments and dyes, or organic or inorganic fine particles.

Examples of dyes include benzeneazo dyes and anthraquinone dyes.

Examples of pigments include black organic pigments such as carbon black, benzofuranone-based black pigments, and perylene-based black pigments, and black inorganic pigments such as fine particles of metals such as titanium, copper, iron, or silver, or oxides and nitrides thereof. , or C.I. I. Pigment Yellow 20, 86, 93, 109, 110, 117, 125, 138, 148, 154, 166, C.I. I. Pigment Orange 36, 43, 51, 61, C.I. I. Pigment Red 9, 97, 122, 149, 168, 177, 180, 192, 217, 220, 228, 240, C.I. I. Pigment Violet 19, 23, 30, 40, 50, C.I. I. Pigment Blue 15, 15:1, 15:4, 22, 60, 64, C.I. I. Pigment Green 7, C.I. I. Pigment Brown 23, 25, 26 and the like.

The coloring agent contains pigments, dyes, etc. When the component (b) is a coloring agent, it is preferably fine particles containing pigments.

Depending on the structure, the fine particles of the component (b) may impart stability such as solvent resistance and heat resistance to the resist film, and optical properties such as transparency, light diffusion and refractive index control.

The fine particles of the component (b) are not particularly limited as long as they fulfill the above-mentioned role, and examples thereof include organic fine particles and inorganic fine particles.

The shape of the organic fine particles and inorganic fine particles is not particularly limited, but may be, for example, a nearly spherical bead shape, a chain shape in which beads are linked, or an irregular shape such as powder.

The average particle size of the organic fine particles used in the present invention is preferably 5 nm to 1000 nm. Here, the average particle diameter (μm) is a 50% volume diameter (median diameter) obtained by measurement by a laser diffraction/scattering method based on Mie theory.

Examples of the organic fine particles include polymethyl methacrylate particles (PMMA particles), silicone particles, polystyrene particles, polycarbonate particles, acrylic styrene particles, benzoguanamine particles, melamine particles, polyolefin particles, polyester particles, polyamide particles, polyimide particles, polyfluoride particles. ethylene chloride particles, and the like.

Commercially available organic fine particles can be suitably used, for example, Techpolymer (registered trademark) MBX series, SBX series, MSX series, SMX series, SSX series, BMX series, ABX series, ARX series, AFX series, MB series, MBP series, MB-C series, ACX series, ACP series [manufactured by Sekisui Plastics Co., Ltd.]; Tospearl (registered trademark) series [Momentive Performance Materials Japan (same)]; Eposter (registered trademark) series, MA series, ST series, MX series [manufactured by Nippon Shokubai Co., Ltd.]; Optobeads (registered trademark) series [ Nissan Chemical Co., Ltd.]; Flowbead series [Sumitomo Seika Co., Ltd.]; Trepal (registered trademark) PPS, PAI, PES, EP [all manufactured by Toray Industries]; 3M (registered trademark) ) Dynion TF micro powder series [manufactured by 3M]; Chemisnow (registered trademark) MX series, MZ series, MR series, KMR series, KSR series, MP series, SX series, SGP series Soken Chemical Co., Ltd.]; C series, WS series [manufactured by Toyobo Co., Ltd.]; Artpearl (registered trademark) GR series, SE series, G series, GS series, J series, MF series, BE series , manufactured by Neagari Kogyo Co., Ltd.]; Shin-Etsu Silicone (registered trademark) KMP series [manufactured by Shin-Etsu Chemical Co., Ltd.].

Examples of the inorganic fine particles include silica, aluminum oxide, aluminum hydroxide, talc, calcium carbonate, mica, magnesium hydroxide, tin oxide, zirconium oxide, titanium oxide, and composite oxides containing these.

Among these inorganic fine particles, silica, zirconium oxide, and titanium oxide are preferred.
Particles having an average primary particle diameter of 5 nm to 100 nm are particularly preferred. Here, the average primary particle size is the average value of primary particle sizes measured by transmission electron observation.

Silica sol can be used as the colloidal silica particles among the particles described above. The silica sol can be an aqueous silica sol produced by a known method using an aqueous sodium silicate solution as a raw material, or an organic solvent-dispersed silica sol obtained by replacing water, which is the dispersion medium of the aqueous silica sol, with an organic solvent.

In addition, alkoxysilanes such as methyl silicate and ethyl silicate are hydrolyzed in an organic solvent such as alcohol in the presence of a catalyst (for example, ammonia, an organic amine compound, an alkali catalyst such as sodium hydroxide), and are obtained by condensation. A silica sol or an organosilica sol obtained by replacing the dispersion medium of the silica sol with another organic solvent can also be used.
Commercially available examples of the organosilica sol include, for example, trade name MA-ST-S (methanol-dispersed silica sol, manufactured by Nissan Chemical Industries, Ltd.), trade name MT-ST (methanol-dispersed silica sol, manufactured by Nissan Chemical Industries, Ltd.), Trade name MA-ST-UP (methanol-dispersed silica sol, manufactured by Nissan Chemical Co., Ltd.), trade name MA-ST-M (methanol-dispersed silica sol, manufactured by Nissan Chemical Co., Ltd.), trade name MA-ST-L (methanol-dispersed Silica sol, manufactured by Nissan Chemical Co., Ltd.), trade name IPA-ST-S (isopropanol-dispersed silica sol, manufactured by Nissan Chemical Co., Ltd.), trade name IPA-ST (isopropanol-dispersed silica sol, manufactured by Nissan Chemical Co., Ltd.), trade name IPA-ST-UP (isopropanol-dispersed silica sol, manufactured by Nissan Chemical Industries, Ltd.), trade name IPA-ST-L (isopropanol-dispersed silica sol, manufactured by Nissan Chemical Industries, Ltd.), trade name IPA-ST-ZL (isopropanol-dispersed silica sol, Nissan Chemical Co., Ltd.), trade name NPC-ST-30 (n-propyl cellosolve dispersion silica sol, Nissan Chemical Co., Ltd.), trade name PGM-ST (1-methoxy-2-propanol dispersion silica sol, Nissan Chemical ( Ltd.), trade name DMAC-ST (dimethylacetamide-dispersed silica sol, manufactured by Nissan Chemical Industries, Ltd.), trade name XBA-ST (xylene/n-butanol mixed solvent-dispersed silica sol, manufactured by Nissan Chemical Co., Ltd.), trade name EAC-ST (ethyl acetate dispersed silica sol, manufactured by Nissan Chemical Co., Ltd.), trade name PMA-ST (propylene glycol monomethyl ether acetate dispersed silica sol, manufactured by Nissan Chemical Co., Ltd.), trade name MEK-ST (methyl ethyl ketone dispersed silica sol, Nissan Chemical Co., Ltd.), trade name MEK-ST-UP (methyl ethyl ketone dispersed silica sol, manufactured by Nissan Chemical Co., Ltd.), trade name MEK-ST-L (methyl ethyl ketone dispersed silica sol, manufactured by Nissan Chemical Co., Ltd.) and trade name MIBK -ST (methyl isobutyl ketone-dispersed silica sol, manufactured by Nissan Chemical Industries, Ltd.) and the like, but are not limited thereto.

Examples of particles of zirconium oxide and composite oxides containing zirconium oxide among the above-mentioned particles include nano-use ZR-40BL (water-dispersed zirconia sol), nano-use OZ-S30M (methanol-dispersed zirconia sol), nano-use OZ-S30K ( methyl ethyl ketone dispersed zirconia sol), Nanouse OZ-S40K-AC (methyl ethyl ketone dispersed zirconia sol), Sancolloid HZ-400M7 (methanol dispersed zirconia sol) (all trade names, manufactured by Nissan Chemical Industries, Ltd.), etc. , but not limited to.

Examples of the particles of titanium oxide and composite oxides containing titanium oxide among the above-mentioned particles include, for example, Sancolloid HT-R305M7-20 (trade name: methanol-dispersed titania sol, manufactured by Nissan Chemical Industries, Ltd.). but not limited to this.

These organic and inorganic fine particles may be used singly or in combination of two or more.

The content of component (b) in the second photosensitive resin composition of the present invention is component (a), component (d) described later, component (e), component (f), component (h) and component (q). ) is preferably 5 to 1000 parts by mass, more preferably 10 to 500 parts by mass, still more preferably 10 to 200 parts by mass when the total mass of the components is 100 parts by mass. If the content of component (b) is less than 5 parts by mass, desired properties such as coloration, improved stability, and control of optical properties may not be obtained. Moreover, when the content of the component (b) is more than 1000 parts by mass, the film formability of the resist film may deteriorate.

<(c) component>
Component (c) used in the present invention includes components (a) and (b) as solvents, and if necessary, components (d), (e), (f), (g), ( It dissolves the components h) and (q) and also dissolves the other additives described below that are added if desired. It is not limited.

Examples of such component (c) include the same component (C) used in the upper layer film-forming composition described above.

These solvents can be used singly or in combination of two or more.
Among these components (c), solvents that do not have a hydroxyl group because they do not dissolve the lower layer film, i.e., methyl cellosolve acetate, ethyl cellosolve acetate, 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, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3- Ethyl ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone and the like are preferred. These solvents are commonly used as solvents for photoresist materials.
When a solvent having a hydroxy group is used, it is preferable to use it in combination with a solvent having no hydroxy group from the viewpoint of not dissolving the lower layer film as described above. Solvents to be combined are not particularly limited, and may be one type or two or more types as long as they have good coating properties and do not dissolve the underlying film. In this case, from the viewpoint of not dissolving the underlayer film, the amount of the solvent having a hydroxyl group is preferably 70% by weight or less, more preferably 60% by weight or less, still more preferably 50% by weight or less, with respect to the entire component (c). Weight percent or less is most preferred.

<(d) component>
Examples of the photosensitive agent as the component (d) include (d-1) a 1,2-quinonediazide compound, (d-2) a photoradical generator, and (d-3) a photoacid generator.

(d-1) As the 1,2-quinonediazide compound, the same compounds as (D-1) listed in the component (D) used in the upper layer film-forming composition can be mentioned.

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

When the second photosensitive resin composition of the present invention is a positive photosensitive resin composition, the content of the compound having a quinonediazide group as component (d-1) is It is preferably 5 to 100 parts by mass, more preferably 8 to 50 parts by mass, still more preferably 10 to 40 parts by mass, based on 100 parts by mass of components h) in total. If the amount is less than 5 parts by mass, the difference in dissolution rate in the developer between the exposed area and the unexposed area of the positive photosensitive resin composition becomes small, and patterning by development may be difficult. On the other hand, if the amount exceeds 100 parts by mass, the 1,2-quinonediazide compound may not be sufficiently decomposed by exposure in a short time, resulting in a decrease in sensitivity, or the component (d-1) may absorb light, resulting in formation of a cured film. It may reduce transparency.

(d-2) The photo-radical generator is not particularly limited as long as it generates radicals upon exposure. Specific examples are the same as (D-2) listed in the component (D) used in the composition for forming the upper layer film.

When the second photosensitive resin composition of the present invention contains component (d-2), the content is from 0.1 part by mass to 100 parts by mass in total of component (a) and component (h). It is preferably 30 parts by mass, more preferably 0.5 to 20 parts by mass, and particularly preferably 1 to 15 parts by mass. If this ratio is too small, the exposed portion may be insufficiently cured, and the pattern may not be formed, or even if it is formed, the film may be unreliable. On the other hand, if this ratio is excessively high, the transmittance of the coating film may be lowered, or development failure may occur in the unexposed areas.

The photoacid generator (d-3) is not particularly limited as long as it is a compound that photodecomposes upon irradiation with ultraviolet rays to generate an acid. As the acid generated when the photoacid generator is photolyzed, when the photoacid generator listed in (D-3) of the component (D) used in the upper layer film forming composition is photolyzed. The same as the acid generated in

Examples of the photoacid generator include the same photoacid generators listed in (D-3) of the component (D) used in the composition for forming the upper layer film.

When the second photosensitive resin composition of the present embodiment contains component (d-3), the content is preferably 0 with respect to a total of 100 parts by mass of components (a) and (h). 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, even more preferably 0.5 to 8 parts by mass. By setting the content of component (d-3) to 0.01 parts by mass or more, sufficient thermosetting and solvent resistance can be imparted. However, if the amount is more than 20 parts by mass, the unexposed area may be poorly developed, or the storage stability of the composition may be lowered.

<(e) component>
Component (e) is a cross-linking agent, which is introduced into the composition when the second photosensitive resin composition of the present invention satisfies the requirement (z1). More specifically, it is a compound having a structure capable of forming a crosslinked structure by thermal reaction with the heat-reactive site (eg, carboxyl group and/or phenolic hydroxy group) of component (a). Specific examples are given below, but are not limited to these. The thermal cross-linking agent is selected from, for example, (e1) a cross-linking compound having two or more substituents selected from alkoxymethyl groups and hydroxymethyl groups and (e2) a cross-linking compound represented by the following formula (2). is preferred. These cross-linking agents can be used alone or in combination of two or more.

The crosslinkable compound (e1) having two or more substituents selected from alkoxymethyl groups and hydroxymethyl groups undergoes a dehydration condensation reaction when exposed to high temperatures during thermosetting. . Such compounds include, for example, compounds such as alkoxymethylated glycoluril, alkoxymethylated benzoguanamine, and alkoxymethylated melamine, and phenoplastic compounds.

As specific examples of the alkoxymethylated glycoluril, the same ones listed as the component (E) used in the upper layer film-forming composition can be used.

As specific examples of the alkoxymethylated benzoguanamine, the same ones listed as the component (E) used in the upper layer film-forming composition can be used.

As specific examples of the phenoplast-based compound, the same compounds as those listed in the component (E) used in the upper layer film-forming composition can be used.

Furthermore, as the component (e1), an acrylamide compound substituted with a hydroxymethyl group or an alkoxymethyl group such as N-hydroxymethylacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethylacrylamide, N-butoxymethylmethacrylamide, or Polymers made using methacrylamide compounds can also be used.

As such a polymer, the same polymer as (E1) listed in the component (E) used in the upper layer film-forming composition can be used.

In the second photosensitive resin composition of the present invention, as the component (e2), the same component (E2) as the component (E) used in the upper layer film-forming composition can be used. .

In addition, as the e component, a thermally reactive site (e.g., carboxyl group and/or phenolic hydroxy group) of the component (a) other than those shown as the (e1) component and the (e2) component is crosslinked by thermal reaction. can also be used. Specifically, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexane. diol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N,N,N',N', -tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, and N,N,N',N',-tetraglycidyl-4,4'-diaminodiphenylmethane, etc. Epoxy compound, VESTANAT B1358/100, VESTAGON BF 1540 (above, isocyanurate-type modified polyisocyanate, manufactured by Degussa Japan Co., Ltd.), Takenate (registered trademark) B-882N, Takenate B-7075 (above, isocyanurate-type modified Examples include isocyanate compounds such as polyisocyanate and Mitsui Chemicals, Inc.).

Also, as the component e, a polymer having two or more structures capable of forming a cross-linked structure by thermal reaction with the heat-reactive sites (e.g., carboxyl groups and/or phenolic hydroxy groups) of the component (a) should be used. can be done. Specifically, for example, polymers produced using compounds having an epoxy group such as glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3-methacryloxypropyltrimethoxy Polymer produced using a compound having an alkoxysilyl group such as silane, 2-isocyanatoethyl methacrylate (Karenzu MOI [registered trademark], manufactured by Showa Denko Co., Ltd.), 2-isocyanatoethyl acrylate (Karenzu AOI [ registered trademark], manufactured by Showa Denko Co., Ltd.), or 2-(0-[1′-methylpropylideneamino]carboxyamino)ethyl methacrylate (KarenzuMOI-BM [registered trademark], Showa Denko Co., Ltd.), 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate (Karenzu MOI-BP [registered trademark], Showa Denko Co., Ltd.) and other compounds having a blocked isocyanate group. Polymers made using These compounds may be used singly or in combination to produce a polymer, or may be combined with other compounds to produce a polymer.

(a) When the component has at least one group that reacts with a group selected from the group consisting of a hydroxyl group, a carboxyl group, an amido group, and an amino group, a hydroxyl group, a carboxyl group, an amido group, 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 component (e) is selected as the cross-linking agent in the second photosensitive resin composition of the present invention, the content is 1 part by mass to 50 parts by mass per 100 parts by mass of components (a) and (h). Part by mass, preferably 1 to 40 parts by mass, 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 the effect of improving heat resistance after pattern formation, solvent resistance, resistance to long-term baking, etc. may not be obtained. On the other hand, if it exceeds 50 parts by mass, uncrosslinked crosslinkable compounds are present, and the heat resistance after pattern formation, solvent resistance, resistance to long-term baking, etc. are lowered, and the photosensitive resin composition is also deteriorated. storage stability may deteriorate.

<(f) component>
Component (f) is a compound having two or more ethylenically polymerizable groups. The term "compound having two or more ethylenically polymerizable groups" as used herein means a compound having two or more polymerizable groups in one molecule and having those polymerizable groups at the ends of the molecule. , the polymerizable group means at least one polymerizable group selected from the group consisting of an acrylate group, a methacrylate group, a vinyl group and an allyl group.
The compound having two or more ethylenically polymerizable groups, which is the component (f), is compatible with each component in the solution of the negative photosensitive resin composition in the second photosensitive resin composition of the present invention. A compound having a molecular weight (weight-average molecular weight when the compound is a polymer) of 1,000 or less is preferred from the viewpoint of good performance and no influence on developability.

Specific examples of such compounds are the same as those listed in the component (F) used in the upper layer film-forming composition described above.

When the second photosensitive resin composition of the present invention contains the component (f), the content is 5 parts by mass to 200 parts by mass with respect to 100 parts by mass of the total of the components (a) and (h). is preferably 10 to 150 parts by mass, and particularly preferably 50 to 150 parts by mass. If this ratio is too small, the exposed portion will be insufficiently cured, and there is a possibility that the pattern cannot be formed, or even if it is formed, the film will be unreliable. If this ratio is too high, tackiness may occur in the pre-baked coating film, or the unexposed portion may become poorly dissolved during development.

<(g) component>
The component (g) used in the second photosensitive resin composition used in the present invention is a compound having two or more functional groups that form a covalent bond with an acid. As such a functional group that forms a covalent bond with an acid, the same functional groups as listed in the component (G) used in the upper layer film-forming composition can be used.

When the second photosensitive resin composition used in the present invention contains a compound having two or more functional groups that form a covalent bond with an acid as component (g), the content of component (a) and component (h) is It is preferably 5 to 200 parts by weight, more preferably 50 to 150 parts by weight based on 100 parts by weight of the total of the components. If this ratio is too small, the photocurability of the negative photosensitive resin composition may be lowered, while if it is too large, the developability of the unexposed area is lowered, resulting in residual film or residue. It may be the cause.

<(h) component>
Component (h) is a polymer having a liquid-repellent group (h1).

In the present invention, the polymer includes, for example, polyimide, polyamic acid, polyamide, polyurea, polyurethane, phenol resin, epoxy resin, polysiloxane, polyester, acrylic polymer, etc. Preferred polymer is acrylic polymer. is mentioned.

Here, the acrylic polymer is obtained using a monomer having a polymerizable unsaturated group such as acrylic acid ester, methacrylic acid ester, styrene, maleimide, etc., that is, a polymerizable group containing a C=C double bond in its structure. It refers to a polymer that is

Polyamic acid, polyimide, polyamide, and polyurea include polyamic acid obtained by reacting diamine with acid dianhydride, polyimide obtained by imidizing the polyamic acid, and polyamide or diamine obtained by reacting diamine with dicarboxylic acid anhydride. is a polyurea obtained by reacting with a diisocyanate, and is 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.

Polyurethanes include polyurethanes obtained by reacting a diol having a fluoroalkyl group or a fluoroalkoxy group and a diol having an amino group with a diisocyanate.

Phenolic resins include novolak resins obtained by polymerizing phenol having a fluoroalkyl group or fluoroalkoxy group with formaldehyde.

Epoxy resins include epoxy resins obtained by reacting bisphenol A and/or bisphenol F having a fluoroalkyl group or fluoroalkoxy group with glycidyl ether of the bisphenol A and/or bisphenol F.

As the polysiloxane, a silane monomer mixture containing a trialkoxysilane having a fluoroalkyl group or a dialkoxysilane having a fluoroalkyl group and a trialkoxysilane having an amino group or a dialkoxysilane having an amino group is polymerized. The polymer obtained is mentioned.

Examples of polyesters include polyesters obtained by reacting a dicarboxylic acid or tetracarboxylic dianhydride with a diol having a fluoroalkyl group or a fluoroalkoxy group.

<(h1) Introduction of Liquid Repellent Group>
Examples of the liquid-repellent group include at least one group selected from fluoroalkyl groups having 3 to 10 carbon atoms, polyfluoroether groups, silyl ether groups and polysiloxane groups.

The fluoroalkyl group has 3 to 10 carbon atoms, preferably 4 to 10 carbon atoms.
Such fluoroalkyl groups include 2,2,2-trifluoroethyl group, 2,2,3,3,3-pentafluoropropyl group, 2-(perfluorobutyl)ethyl group, 3-perfluorobutyl -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, and the like.

In order to introduce a fluoroalkyl group having 3 to 10 carbon atoms into the polymer which is the component (h) 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 (h) is an acrylic polymer include 2,2,2-trifluoroethyl acrylate, 2,2,2-trifluoroethyl acrylate, 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-(perfluoro-3-methylbutyl) 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)- 2-hydroxypropyl acrylate, 2-(perfluoro-7-methyloctyl)-2-hydroxypropyl methacrylate, and the like.

Examples of the polyfluoroether group include an Rf group having a polyfluoroether structure represented by Formula 3 below.
-(X-O) _n -Y Formula 3
In formula 3, X is a divalent saturated hydrocarbon group having 1 to 10 carbon atoms or a fluorinated divalent saturated hydrocarbon group having 1 to 10 carbon atoms, and each unit enclosed by n represents the same group or a different group, Y is a hydrogen atom (limited to the case where no fluorine atom is bonded to the carbon atom adjacent to the oxygen atom adjacent to Y), or a monovalent saturated carbon atom having 1 to 20 carbon atoms represents a hydrogen group or a fluorinated monovalent saturated hydrocarbon group having 1 to 20 carbon atoms; n represents an integer of 2 to 50; However, the total number of fluorine atoms in Formula 3 is 2 or more.

As aspects of X and Y in Formula 3, X is preferably an alkylene group having 1 to 10 carbon atoms and fluorinated by removing one hydrogen atom, or a perfluorinated alkylene group having 1 to 10 carbon atoms. group, wherein each unit enclosed by n represents the same group or a different group, and Y is an alkyl group having 1 to 20 carbon atoms and fluorinated by removing one hydrogen atom, or 1 carbon atom to 20 perfluorinated alkyl groups.

As aspects of X and Y in Formula 3, more preferably, X is a perfluorinated alkylene group having 1 to 10 carbon atoms, and each unit enclosed by n is the same group or a different group. and Y represents a perfluorinated alkyl group having 1 to 20 carbon atoms.

In Formula 3, n represents an integer from 2 to 50. n is preferably 2 to 30, more preferably 2 to 15. Liquid repellency is favorable in n being two or more. When n is 50 or less, the polymer (A) is a monomer having an Rf group, a hydroxyl group, a carboxyl group, an amide group, an amino group, an N-alkoxymethylamide group, a blocked isocyanate group or a trialkoxy group. The compatibility of the monomers is improved when the compound is synthesized by copolymerization with a monomer having a silyl group or other monomers.

The total number of carbon atoms in the Rf group having the polyfluoroether structure represented by Formula 3 is preferably 2 to 50, more preferably 2 to 30. Within this range, the polymer as component (h) exhibits good liquid repellency. Further, the polymer as the component (h) is a monomer having an Rf group, and a monomer having a hydroxyl group, a carboxyl group, an amide group, an amino group, an N-alkoxymethylamide group, a blocked isocyanate group or a trialkoxysilyl group. When synthesized by copolymerization with other monomers, the compatibility of the monomers is improved.

Specific examples of X include -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 , _- ( _CF2 ) _{5CF3 ,} -( _CF2 ) _6CF3 , -( _CF2 ) _{7CF3 ,} -( _CF2 ) _{8CF3 ,} -( _CF2 ) _{9CF3 ,} and ( _CF2 ) ₁₁ CF ₃ , —(CF ₂ ) ₁₅ CF ₃ .

A preferred embodiment of the Rf group having a polyfluoroether structure represented by Formula 3 includes an Rf group represented by Formula 4.
−C _p−1 F _2(p−1) −O−(C _p F _2p −O) _n−1 −C _q F _2q+1 Formula 4
In Formula 4, p is an integer of 2 or 3, each unit enclosed by n is the same group, q is an integer of 1 to 20, and n is an integer of 2 to 50.

As the Rf group represented by Formula 4, specifically,
- CF ₂ O(CF ₂ CF ₂ O) _n-1 CF ₃ (n is 2 to 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 preferred from the viewpoint of ease of synthesis.

The Rf groups in the polymer of component (h) may all be the same or different.

The silyl ether group means a group in which the hydroxyl group of alcohol is protected with a trialkylsilyl group, preferably a group represented by the following formula.
^-X4 -Si ₍ ^O - ^SiX1X2X3 ) ³
(In the formula, X ¹ , X ² and X ³ each 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 (h) of the present invention, a monomer having a silyl ether group may be copolymerized.

When the component (h) is an acrylic polymer, examples of monomers having a silyl ether group include methacryloxypropyltris(trimethylsiloxy)silane and acryloxypropyltris(trimethylsiloxy)silane.

Examples of the polysiloxane group include groups having a polysiloxane structure represented by Formula 5. Hereinafter, a group having a polysiloxane structure represented by Formula 5 is referred to as a pSi group.
—(SiR ¹ R ² —O) _n —SiR ¹ R ² R ³ Formula 5
(where R ¹ and R ² independently represent a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group; R ³ represents hydrogen or an organic group having 1 to 10 carbon atoms; n is an integer of 1 to 200; represents ).

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 siloxy unit. R ¹ and R ² are preferably hydrogen, ^a methyl group or a phenyl group because the polymer of component (h) exhibits good liquid repellency ^. is preferably a methyl group. In addition, R ³ may contain a nitrogen atom, an oxygen atom, or the like.

Methods for introducing the pSi group into the polymer (h) include methods of copolymerizing a monomer having a pSi group, various modification methods of reacting a polymer having a reaction site with a compound having a pSi group, and A method of using a polymerization initiator having

Monomers having a pSi group include CH ₂ ═CHCOO(pSi), CH ₂ ═C(CH ₃ )COO(pSi), and the like. However, pSi represents a pSi group. Monomers having a pSi group may be used alone, or two or more of them may be used in combination.

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

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

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

The polymerization initiator having a pSi group may contain a group having a divalent polysiloxane structure in the main chain of the initiator molecule, or may contain a monovalent polysiloxane in the terminal portion or side chain of the initiator molecule. A group having a structure may be included. Initiator The initiator containing a group having a divalent polysiloxane structure in its molecular main chain includes, for example, a compound having a group having a divalent polysiloxane structure and an azo group alternately. Commercially available products include VPS-1001 and VPS-0501 (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.).

Component (h) is preferably a polymer further containing (h2): a group selected from an N-alkoxymethylamide group, a blocked isocyanate group and a trialkoxysilyl group.

<(h2): Introduction of group selected from N-alkoxymethylamide group, blocked isocyanate group and trialkoxysilyl group>
In order to introduce a group selected from an N-alkoxymethylamide group, a blocked isocyanate group and a trialkoxysilyl group into the polymer as component (h), an N-alkoxymethylamide group, a blocked isocyanate group and a trialkoxysilyl group A monomer having a selected group may be copolymerized.

Examples of monomers having an N-alkoxymethylamide group when the component (h) is an acrylic polymer include N-hydroxymethyl (meth)acrylamide, N-methoxymethyl (meth)acrylamide, N-ethoxymethyl (meth)acrylamide, ) hydroxymethyl- or alkoxymethyl-substituted (meth)acrylamide compounds such as acrylamide and N-butoxymethyl(meth)acrylamide.

Examples of monomers having a blocked isocyanate group when the component (h) is an acrylic polymer include 2-(0-(1′-methylpropylideneamino)carboxyamino)ethyl methacrylate, 2-(3 ,5-dimethylpyrazolyl)carbonylamino)ethyl and the like.

Monomers having a trialkoxysilyl group when the component (h) is an acrylic polymer include, for example, 3-trimethoxysilylpropyl acrylate, 3-triethoxysilylpropyl acrylate, 3-trimethoxysilylpropyl methacrylate, 3- and triethoxysilylpropyl methacrylate.

Component (h) is preferably a polymer having at least one group selected from the group consisting of (h3) hydroxy group, carboxyl group, amide group and amino group.

<(h3) Introduction of at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group and an amino group>
In order to introduce at least one group selected from the group consisting of (h3) a hydroxy group, a carboxyl group, an amide group and an amino group into the polymer that is the component (h) of the present invention, (h3) a hydroxy group, a carboxyl group , an amide group and an amino group.

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

When the component (h) is an acrylic polymer, examples of monomers having a hydroxy group include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylates, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate, glycerin monomethacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, caprolactone 2-(acryloyloxy) ethyl ester, caprolactone 2-( methacryloyloxy)ethyl ester, poly(ethylene glycol) acrylate, poly(propylene glycol) acrylate, poly(ethylene glycol) ethyl ether acrylate, poly(ethylene glycol) ethyl ether methacrylate, 5-acryloyloxy-6-hydroxynorbornene-2- Carboxylic-6-lactone and 5-methacryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone, p-hydroxystyrene, α-methyl-p-hydroxystyrene, N-hydroxyphenylmaleimide, N-hydroxy Phenyl acrylamide, N-hydroxyphenyl methacrylamide, p-hydroxyphenyl acrylate, p-hydroxyphenyl methacrylate and the like. Among them, monomers selected from 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate are preferred.

When the component (h) is an acrylic polymer, examples of monomers having an amide group include acrylamide, methacrylamide, N-methylacrylamide, N,N-dimethylacrylamide and N,N-diethylacrylamide. Among them, methacrylamide is preferred.

When the component (h) is an acrylic polymer, the amino group-containing monomer includes, for example, aminoethyl acrylate, aminoethyl methacrylate, aminopropyl acrylate, and aminopropyl methacrylate.

When the component (h) is an acrylic polymer, the method for producing the polymer of the component (h) includes a monomer having a liquid-repellent group, such as a monomer having a fluoroalkyl group having 3 to 10 carbon atoms, a monomer having a polyfluoroether group, a monomer having at least one group selected from the group consisting of an N-alkoxymethylamide group, a blocked isocyanate group and a trialkoxysilyl group, optionally a hydroxy group, a carboxyl group, an amide group and A monomer having at least one group selected from the group consisting of amino groups, and optionally a further monomer other than the above (hereinafter also referred to as other monomer A) are heated in a solvent in the presence of a polymerization initiator at 50°C to 110°C. obtained by polymerizing at a temperature of At that time, the solvent to be used is not particularly limited as long as it dissolves the monomers constituting the alkali-soluble polymer and the polymer having the specific functional group. Specific examples include the solvents described in component (c) above.

Specific examples of other monomers h include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, glycidyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, and 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-tricyclodecyl 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, isobornyl 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-8-tri Cyclodecyl acrylate, 8-ethyl-8-tricyclodecyl acrylate, N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, styrene, vinylnaphthalene, vinylanthracene, and vinylbiphenyl. .

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

In addition, the solution of the specific copolymer obtained as described above is added to diethyl ether, water, or the like under stirring to reprecipitate, and after filtering and washing the generated precipitate, 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 unreacted monomers coexisting with the specific copolymer can be removed, and as a result, a purified powder of the specific copolymer can be obtained. If the purification cannot be sufficiently performed in 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 the above-mentioned component (c) and used in the form of a solution.

In the polymer of the component (h), the amount of the liquid-repellent group (h1) introduced is preferably 5 mol% to 60 mol%, more preferably 5 mol% to 40 mol%, based on the total repeating units. is more preferable. If the amount is less than 5 mol %, the liquid-repellent effect may not be obtained. If it is more than 60 mol %, problems such as aggregation may occur.

In the polymer of component (h), the introduced amount of the group (h2) selected from N-alkoxymethylamide groups, blocked isocyanate groups and trialkoxysilyl groups is 5 mol% to 70 mol% of all repeating units. and more preferably 5 mol % to 50 mol %. If the amount is less than 5 mol %, problems may arise in the heat resistance and solvent resistance of the resulting film. If it is more than 60 mol %, it may affect developability.

When introducing at least one group (h3) selected from the group consisting of a hydroxy group, a carboxyl group, an amide group and an amino group in the polymer of component (h) above, the amount introduced is based on all repeating units. It is preferably 5 mol % to 60 mol %, more preferably 5 mol % to 40 mol %. If it is less than 5 mol %, the effect of improving the heat resistance and solvent resistance of the obtained film may not be obtained. If it is more than 60 mol %, the number of liquid-repellent repeating units will be too small.

The number average molecular weight of the polymer of component (h) is preferably from 2,000 to 100,000. More preferably 3,000 to 50,000, still more preferably 4,000 to 10,000. A number average molecular weight greater than 100,000 may result in residue.

In the present invention, the polymer of component (h) may be a mixture of a plurality of specific copolymers.

The ratio of component (h) to component (a) is 0.1 to 20 parts by mass of component (h) per 100 parts by mass of component (a).

When component (a) has a liquid-repellent group (h1) in component (h), component (a) can also serve as component (h), and in this case component (h) does not necessarily have to be used. do not have.
In this case, it is preferable that polymerized units (monomers) having a liquid-repellent group (h1) account for 5 to 30 parts by weight in 100 parts by weight of component (a).

<Other additives>
Furthermore, the second photosensitive resin composition used in the present invention may optionally contain a leveling agent, a surfactant, a rheology modifier, a storage stabilizer, an antifoaming agent, as long as the effects of the present invention are not impaired. Adhesion promoters or dissolution promoters such as polyhydric phenols and polyhydric carboxylic acids may be contained.
As the surfactant, the same surfactants as listed in <Other Additives> used in the upper layer film-forming composition can be used.
In order to play the role of liquid repellency, the surfactant may be used together with component (h), or may be used alone.

<Bank forming process>
After the resist film 13 is formed, the underlying film 12 and the resist film 13 are collectively patterned by exposing and developing to form a bank. A region (non-bank portion) partitioned by the bank is formed in the opening 14 (see FIG. 1).

As shown in FIG. 1, when the first and second photosensitive resin compositions are positive-working photosensitive resin compositions, the exposed portion is the non-bank portion, and the lower layer of the non-bank portion is formed during the development process. It is removed together with the film and the resist film in the non-bank portion to form the opening 14 . Alternatively, when the first and second photosensitive resin compositions of the present invention are negative photosensitive resin compositions, the exposed portion becomes the bank portion, and in the development process, the lower layer film of the non-bank portion and the non-bank portion are formed. It is removed together with the resist film of the part.

A conventional second photosensitive resin composition leaves a residue in the development process, which is difficult to cleanly remove. The remaining residue causes defects such as unevenness in the organic thin film in the process of further forming the organic thin film in the regions partitioned by the banks. If the bank is formed by the bank pattern forming method of the present invention, a clean organic thin film can be formed because it is difficult for residues to remain on the substrate or on other layers intervening on the substrate.

Here, other layers that can be formed on the substrate 11 include, for example, an anode, a cathode, a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, and a block layer in the case of an organic electroluminescence device. , a light-emitting layer, and the like. When the method for forming a bank pattern of the present invention is used for an organic electroluminescent device, the hole injection layer of organic electroluminescence is particularly suitable as the other layer. The other layer consists of at least one layer.

<Photosensitive resin composition>
The first photosensitive resin composition used in the present invention is a photosensitive resin composition containing the following components (A), (C) and (D), and if desired, the component (E) a cross-linking agent, a compound having two or more ethylenically polymerizable groups as component (F), a compound having two or more functional groups that form covalent bonds with an acid as component (G), and other additives. It is a composition that can contain further.
(A) component: an alkali-soluble resin having an amide group,
(C) component: solvent,
(D) Component: Photosensitizer.

Among them, preferred examples of the first photosensitive resin composition used in the present invention are as follows.
[1]: A photosensitive resin composition containing 5 to 100 parts by mass of component (D) per 100 parts by mass of component (A), wherein these components are dissolved in component (C), and The first photosensitive resin composition, wherein the component (D) is the component (D-1).
[2]: A photosensitive resin composition containing 5 parts by mass to 100 parts by mass of component (D) per 100 parts by mass of component (A), these components being dissolved in component (C), Furthermore, a photosensitive resin composition containing 1 to 50 parts by mass of a crosslinking agent as component (E) with respect to 100 parts by mass of component (A), wherein the component (D) is (D-1 ) component of the first photosensitive resin composition.
[3]: 5 parts by mass to 200 parts by mass of component (F) per 100 parts by mass of component (A), and 0.1 part by mass per 100 parts by mass of the total of components (A) and (F) to 30 parts by mass of the component (D), a photosensitive resin composition in which these are dissolved in the component (C), and the component (D) is the component (D-2). A photosensitive resin composition.

The proportion of solids in the first photosensitive resin composition used in the present invention is not particularly limited as long as each component is uniformly dissolved in the solvent. Yes, and for example 5% to 60% by weight, or 10% to 50% by weight. Here, the solid content refers to the total components of the photosensitive resin composition excluding the component (C).

The method for preparing the first photosensitive resin composition used in the present invention is not particularly limited. , to this solution are covalently bonded by the component (D) photosensitive agent, optionally the component (E) cross-linking agent, the component (F) compound having two or more ethylenically polymerizable groups, and the component (G) acid. A method of mixing a compound having two or more functional groups that form a predetermined ratio to form a uniform solution, or in an appropriate stage of this preparation method, further adding and mixing other additives as necessary method.

In preparing the first photosensitive resin composition used in the present invention, the copolymer solution obtained by the polymerization reaction in the component (C) can be used as it is. In this case, the component (A), ( When adding component D and, if necessary, component (E), component (F), component (G), etc. to form a uniform solution, component (C) may be added for the purpose of adjusting the concentration. good. At this time, the component (C) used in the formation process of the specific copolymer and the component (C) used for concentration adjustment during the preparation of the first photosensitive resin composition may be the same. , may differ.

Therefore, the prepared solution of the first photosensitive resin composition is preferably used after being filtered using a filter having a pore size of about 0.2 μm.

The second photosensitive resin composition used in the present invention is a photosensitive resin composition containing the following components (a), (b), (c) and (d), and if desired, Component (e) a cross-linking agent, Component (f) a compound having two or more ethylenically polymerizable groups, Component (g) a compound having two or more functional groups capable of forming a covalent bond with an acid, and Component (h). and/or component (q) and one or more of other additives.
(a) component: alkali-soluble resin,
(b) component: fine particles,
(c) component: solvent,
(d) Component: Photosensitizer.

Preferred examples of the second photosensitive resin composition used in the present invention are as follows.
[1]: A second photosensitive resin composition containing 0.1 to 20 parts by mass of component (h) per 100 parts by mass of component (a) dissolved in component (c) thing.
[2]: 0.1 to 20 parts by mass of component (h) and 5 to 100 parts by mass of component (d) per 100 parts by mass of component (a), and these components contain (c ) component dissolved therein, wherein the component (d) is the component (d-1).
[3]: 0.1 to 20 parts by mass of component (h) and 5 to 100 parts by mass of component (d) per 100 parts by mass of component (a), and these components contain (c ) of the photosensitive resin composition dissolved in the component, and the crosslinking agent as the component (e) is added in an amount of 1 to 50 parts by mass per 100 parts by mass of the total of the components (a) and (h). A second photosensitive resin composition, wherein the component (d) is the component (d-1).
[4]: 0.1 to 20 parts by mass of component (h) per 100 parts by mass of component (a), and 5 to 200 parts by mass of component (a) and component (b) per 100 parts by mass 0.1 to 30 parts by mass of component (d) with respect to 100 parts by mass of the total of component (f), component (a), component (b) and component (f), and these are ( A second photosensitive resin composition which is a photosensitive resin composition dissolved in component c), wherein the component (d) is the component (d-2).
[5]: 100 parts by mass of component (a) containing a liquid-repellent group (h1) and excluding component (h) contains 5 mass of polymer units having a liquid-repellent group (h1) in component (a) A second photosensitive resin composition comprising component (a) in an amount of 1 part to 30 parts by mass.

The proportion of solids in the second photosensitive resin composition used in the present invention is not particularly limited as long as each component is uniformly dissolved in the solvent, but is, for example, 1% by mass to 80% by mass. Yes, and for example 5% to 60% by weight, or 10% to 50% by weight. Here, the solid content refers to the total components of the second photosensitive resin composition excluding the component (c).

The preparation method of the second photosensitive resin composition used in the present invention is not particularly limited, but as a preparation method, for example, (h) component (specific polymer) is dissolved in (c) component, and this solution (a) component alkali-soluble resin, (b) component fine particles, (d) component photosensitive agent, optionally (e) component cross-linking agent, and (f) component two ethylenic polymerizable groups. A method of mixing a compound having the above and a compound having two or more functional groups that form a covalent bond with an acid as component (g) in a predetermined ratio to form a uniform solution, or in an appropriate stage of this preparation method , and a method of further adding and mixing other additives as necessary.

In preparing the second photosensitive resin composition used in the present invention, the solution of the copolymer obtained by the polymerization reaction in component (c) can be used as it is. In the solution, components (a), (d), and, if necessary, components (e), (f), and (g) are added in the same manner as in the first photosensitive resin composition to form a uniform solution. In this case, the component (c) may be additionally added for the purpose of adjusting the concentration. At this time, the component (c) used in the formation process of the specific copolymer and the component (c) used for adjusting the concentration during the preparation of the second photosensitive resin composition may be the same. , may differ.

Therefore, the prepared solution of the second photosensitive resin composition is preferably used after being filtered using a filter having a pore size of about 0.2 μm.

<Coating film and cured film as underlayer film>
The first photosensitive resin composition used in the present invention is applied to semiconductor substrates (e.g., silicon/silicon dioxide coated substrates, silicon nitride substrates, substrates coated with metals (e.g., aluminum, molybdenum, chromium), etc., glass substrates, quartz substrates, etc.). substrate, ITO substrate, etc.) by spin coating, flow coating, roll coating, slit coating, spin coating following the slit, inkjet coating, etc., and then pre-drying on a hot plate or oven, etc. A coating film can be formed. After that, by heat-treating this coating film, a photosensitive resin film is formed as an underlayer film.

As conditions for this heat treatment, for example, a heating temperature and a heating time appropriately selected from the range of a temperature of 70° C. to 160° C. and a time 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 photosensitive resin film formed from the first photosensitive resin composition is, for example, 0.1 μm to 30 μm, or, for example, 0.2 μm to 10 μm, and further, for example, 0.3 μm to 8 μm. be.

<Coating film and cured film as resist film>
The second photosensitive resin composition used in the present invention is coated on the underlayer film obtained above by spin coating, flow coating, roll coating, slit coating, spin coating following the slit, inkjet coating, or the like, After that, a coating film can be formed by pre-drying with a hot plate, an oven, or the like. After that, the coating film is heat-treated to form a photosensitive resin film as a resist film.

As conditions for this heat treatment, for example, a heating temperature and a heating time appropriately selected from the range of a temperature of 70° C. to 160° C. and a time 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 photosensitive resin film formed from the second photosensitive resin composition is, for example, 0.1 μm to 30 μm, for example, 0.2 μm to 10 μm, and further, for example, 0.3 μm to 8 μm. be.

A mask having a predetermined pattern is mounted on the coating film of the underlayer film and the resist film on the underlayer film obtained above, light such as ultraviolet light is irradiated, and development is performed with an alkaline developer to obtain a film depending on the material composition. Either the exposed area or the unexposed area is washed out, and the remaining patterned film is optionally heated at 80° C. to 140° C. for 0.5 to 10 minutes to form a sharp relief pattern on the end face. can get.

Alkaline developers that can be used include, for example, aqueous solutions of alkali metal hydroxides such as potassium carbonate, sodium carbonate, potassium hydroxide, sodium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, hydroxides such as choline Alkaline aqueous solutions such as aqueous solutions of quaternary ammonium, aqueous solutions of amines such as ethanolamine, propylamine and ethylenediamine are included. Furthermore, a surfactant or the like can be added to these developers.

Among the above, 0.1 to 2.58% by mass aqueous solution of tetraethylammonium hydroxide is generally used as a developer for photoresist, and this is also used in the first and second photosensitive resin compositions of the present invention. It can be developed well with an alkaline developer without causing problems such as swelling of the film.

Moreover, as a developing method, any of a liquid heaping method, a dipping method, an oscillating immersion method, and the like can be used. The development time at that time is usually 15 to 180 seconds.

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

Subsequently, the pattern-formed film is post-baked for thermosetting, specifically by heating using a hot plate, an oven, etc., to improve heat resistance, transparency, planarization, A film having low water absorption, excellent chemical resistance, etc., and a good relief pattern can be obtained.

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

Thus, by such post-baking, a desired cured film having a favorable pattern shape can be obtained.

As described above, by the patterning method of the cured film, it is possible to form a liquid-repellent bank pattern in which residues such as components of a liquid-repellent resist material are less likely to remain in areas other than the banks. A uniform organic thin film can be formed.

EXAMPLES The present invention will be described in more detail below with reference to Examples, but the present invention is not limited to these Examples. In addition, the measurement of the molecular weight of the polymer is as follows.
[Measurement of molecular weight of polymer]
Measurement of the molecular weight of the polymer was carried out under the following conditions using a GPC system manufactured by JASCO Corporation as an apparatus and using Shodex (registered trademark) KF-804L and 803L as columns.
Column oven: 40°C
Flow rate: 1 mL/min Eluent: Tetrahydrofuran

Abbreviations used in the following examples have the following meanings.
QDC: 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride MMA: methyl methacrylate HEMA: 2-hydroxyethyl methacrylate HPMA: 4-hydroxyphenyl methacrylate CHMI: N-cyclohexylmaleimide PFHMA: 2-(perfluorohexyl)ethyl Methacrylates TMSSMA: methacryloxypropyltris(trimethylsiloxy)silane KBM-503: 3-methacryloxypropyltriethoxysilane MAA: methacrylic acid MAAm: methacrylamide HPMA-QD: 1 mol of 4-hydroxyphenyl methacrylate and 1,2-naphthoquinone-2 -Compound synthesized by condensation reaction with 1.1 mol of diazido-5-sulfonyl chloride AIBN: α,α'-azobisisobutyronitrile QD1: α,α,α'-tris(4-hydroxyphenyl)-1 -Compound QD2: 4,4′,4″-(3-methyl-1- Compound synthesized by condensation reaction of 1 mol of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride with 1 mol of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride CST: a polymer of 85% hydroxystyrene and 15% styrene, and hydroxy Styrene polymer obtained by mixing 70% styrene and 30% styrene polymer at a ratio of 3:7 (manufactured by Maruzen Petrochemical Co., Ltd.)
8KQ: 8KQ-2001 (manufactured by Taisei Fine Chemical Co., Ltd., alkali-soluble UV curable acrylic resin)
Poly-AA: Polyacrylic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
I907: 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (IRGACURE 907, manufactured by BASF)
DEAB: 4,4'-bis (diethylamino) benzophenone DPHA: dipentaerythritol hexaacrylate OXE-02: IRGACURE OXE-02 (manufactured by BASF)
GT-401: butanetetracarboxylic acid tetra (3,4-epoxycyclohexylmethyl) modified ε-caprolactone YH-434L: YH-434L manufactured by Shin Nikka Epoxy Manufacturing Co., Ltd. (currently Nippon Steel & Sumikin Chemical Co., Ltd.)
CEL-2021P: 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexane carboxylate R-30: Megafac R-30 (manufactured by DIC Corporation)
CB1: Propylene glycol monomethyl ether acetate-dispersed carbon black (manufactured by Mikuni Color Co., Ltd.)
CB2: Carbon black dispersed in propylene glycol monomethyl ether (manufactured by Mikuni Color Co., Ltd.)
TB1: Propylene glycol monomethyl ether acetate dispersed titanium black (manufactured by Mitsubishi Materials Corporation)
PMA-ST: Propylene glycol monomethyl ether acetate-dispersed silica sol (manufactured by Nissan Chemical Industries, Ltd.)
OZ-S30K: Nanouse OZ-S30K (MEK dispersed zirconia sol, manufactured by Nissan Chemical Co., Ltd.)
PGME: Propylene glycol monomethyl ether PGMEA: Propylene glycol monomethyl ether acetate EL: Ethyl lactate CH: Cyclohexanone

<Synthesis Example 1>
3.00 g of MAAm, 3.00 g of HPMA, 4.00 g of CHMI, and 0.8 g of AIBN were dissolved in 43.2 g of PGME and reacted at 80° C. for 20 hours to obtain an acrylic polymer solution (solid concentration: 30% by mass). was obtained (P1). The obtained acrylic polymer had an Mn of 3,000 and an Mw of 6,200.

<Synthesis Example 2>
3.00 g of MAAm, 3.00 g of HPMA, 4.00 g of CHMI, and 0.8 g of AIBN were dissolved in 43.2 g of PGME and reacted at 80° C. for 20 hours to obtain an acrylic polymer solution (solid concentration: 30% by mass). was obtained (P2). The obtained acrylic polymer had an Mn of 3,000 and an Mw of 6,400.

<Synthesis Example 3>
3.00 g of MAAm, 3.00 g of HPMA, 4.00 g of CHMI, and 0.8 g of AIBN were dissolved in 43.2 g of PGME and reacted at 80° C. for 20 hours to obtain an acrylic polymer solution (solid concentration: 30% by mass). was obtained (P3). The obtained acrylic polymer had an Mn of 3,500 and an Mw of 7,500.

<Synthesis Example 4>
An acrylic polymer solution (solid content: concentration of 40% by weight) was obtained (P4). The obtained acrylic polymer had an Mn of 2,400 and an Mw of 4,700.

<Synthesis Example 5>
MAA 90.00g, HEMA 225.00g, HPMA 45.00g, MMA
180.00 g of CHMI, 360.00 g of CHMI, and 57.60 g of AIBN were dissolved in 1436.40 g of PGME and reacted at 80° C. for 20 hours to obtain an acrylic polymer solution (solid concentration: 40% by mass) (P5). . The obtained acrylic polymer had an Mn of 3,100 and an Mw of 6,100.

<Synthesis Example 6>
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 were dissolved in 51.3 g of CH and stirred at 110° C. for 20 hours. An acrylic polymer solution (solid concentration: 20% by mass) was obtained (P6). The obtained acrylic polymer had an Mn of 7,200 and an Mw of 11,000.

Components (A), (D) and (E) and a solvent were mixed according to the composition shown in Table 1 to prepare first photosensitive resin compositions for underlayer film materials 1 to 7.

Similarly, second photosensitive resin compositions of upper resist layer materials 1 to 7 were prepared according to the compositions shown in Table 2. Note that the composition ratios in Tables 1 and 2 represent ratios in terms of solid content.

[Evaluation 1 Evaluation of pattern shape]
After applying the resin compositions of the lower layer materials 1 to 7 onto the ITO-glass substrate using a spin coater, pre-baking is performed on a hot plate at a temperature of 100 ° C. for 120 seconds to form a coating film of the lower layer material with a thickness of 0.2 μm. formed. Next, the photosensitive resin compositions of the upper layer materials 1 to 7 were applied on the lower layer material coating film using a spin coater, and then prebaked on a hot plate at a temperature of 100 ° C. for 120 seconds to obtain a film thickness of 1.1 μm. A coating of overlayer material was formed. The coated film was irradiated with ultraviolet light having a light intensity of 2.6 mW/cm 2 at 365 nm for a certain period of time using a PLA-600FA ultraviolet light irradiation device manufactured by Canon Inc. through a photomask having a line and space pattern of 50 μm drawn thereon. Thereafter, the coating film was immersed in a 2.38% by mass or 0.4% by mass aqueous solution of tetramethylammonium hydroxide (hereinafter referred to as TMAH) for a predetermined period of time, and then washed with running ultrapure water for 30 seconds. Then, this coating film was post-baked by heating it at a temperature of 230° C. for 30 minutes to prepare substrates of Examples 1-7 and Comparative Examples 1-11. In Comparative Examples 1 to 7, substrates were produced in the same manner as described above without performing the coating and prebaking steps of the lower layer materials 1 to 7. The state of the created line & space pattern was observed with an optical microscope. If the pattern was peeled off from the substrate, it was rated as “Peeled”; Table 3 shows the results obtained.

[Evaluation 2 Evaluation of bank part contact angle]
After coating the photosensitive resin composition of the lower layer material 2 on the ITO-glass substrate using a spin coater, pre-baking is performed on a hot plate at a temperature of 100 ° C. for 120 seconds to form a coating film of the lower layer material with a thickness of 0.2 μm. formed. Next, after applying the photosensitive resin composition of the upper layer material 4 on the lower layer material coating film using a spin coater, pre-baking is performed on a hot plate at a temperature of 100 ° C. for 120 seconds to obtain an upper layer material with a thickness of 1.1 μm. to form a coating film. Thereafter, the coating film was immersed in a 2.38% by mass or 0.4% by mass TMAH aqueous solution for a predetermined time, and then washed with running ultrapure water for 30 seconds. Then, this coating film was post-baked by heating it at a temperature of 230° C. for 30 minutes to form a cured film on the ITO-glass substrate of Example 4. In Examples 1 to 3, a cured film was formed on an ITO-glass substrate composed of the upper layer material and the lower layer material in the same manner as described above without UV exposure. In Comparative Example 4, a cured film consisting of only the upper layer material 4 was formed on the ITO-glass substrate in the same manner as described above without performing the lower layer material 2 coating and prebaking steps. The contact angle of anisole on this cured film was measured using Drop Master manufactured by Kyowa Interface Science Co., Ltd. Table 3 shows the results obtained. Evaluation 2 was performed only for Example 4 and Comparative Example 4 containing the component (h) in the upper layer material.

[Evaluation 3 Evaluation of contact angle of exposed area on ITO substrate]
After coating the photosensitive resin composition of the lower layer material 2 on the ITO-glass substrate using a spin coater, pre-baking is performed on a hot plate at a temperature of 100 ° C. for 120 seconds to form a coating film of the lower layer material with a thickness of 0.2 μm. formed. Next, after applying the photosensitive resin composition of the upper layer material 4 on the lower layer material coating film using a spin coater, pre-baking is performed on a hot plate at a temperature of 100 ° C. for 120 seconds to obtain an upper layer material with a thickness of 1.1 μm. to form a coating film. This coating film was irradiated with ultraviolet rays having a light intensity of 2.6 mW/cm 2 at 365 nm for a certain period of time using an ultraviolet irradiation apparatus PLA-600FA manufactured by Canon Inc. Thereafter, the coating film was immersed in a 2.38% by mass or 0.4% by mass TMAH aqueous solution for a predetermined time, and then washed with running ultrapure water for 30 seconds. Then, this coating film was post-baked by heating it at a temperature of 230° C. for 30 minutes to form a cured film on the ITO-glass substrate of Example 4. In Examples 1 to 3, a cured film was formed on an ITO-glass substrate composed of the upper layer material and the lower layer material in the same manner as described above without UV exposure. In Comparative Example 4, a cured film consisting of only the upper layer material 4 was formed on the ITO-glass substrate in the same manner as described above without performing the lower layer material 2 coating and prebaking steps. The contact angle of anisole on this cured film was measured using Drop Master manufactured by Kyowa Interface Science Co., Ltd. Table 3 shows the results obtained. Evaluation 3 was performed only for Example 4 and Comparative Example 4 containing the component (h) in the upper layer material.

As shown in Table 3, in Comparative Examples 1 to 7 in which the lower layer material was not used in Evaluation 1, residues were observed in all of them, whereas in Examples 1 to 7 in which the lower layer material was used, residues were observed in all of them. A good pattern shape was obtained. Further, in Comparative Examples 8 to 11 in which a hydrophilic resin containing no amide group was used as the lower layer material, the pattern peeled off during development in Evaluation 1 and did not remain on the substrate.

Claims (27)

In a method for forming banks and regions defined by the banks on a substrate, the method for forming a bank pattern for forming an organic thin film in the regions defined by the banks, comprising:
Underlayer film formation by coating a first photosensitive resin composition containing the following components (A), (C) and (D) on a substrate directly or via another layer to provide an underlayer film process and
A resist film forming step of applying a second photosensitive resin composition containing the following components (a), (b), (c) and (d) on the underlayer film to form a resist film. and,
a bank forming step of forming banks by exposing and developing the resist film, and removing the lower layer film in the non-bank portions together with the resist film in the non-bank portions during the developing process.
(A) component: an alkali-soluble resin having an amide group (the amide group is derived from at least one monomer selected from acrylamide and methacrylamide);
(C) component: solvent,
(D) component: photosensitizer,
(a) component: alkali-soluble resin,
(b) component: fine particles,
(c) component: solvent,
(d) component: photosensitizer 2. The method of forming a bank pattern according to claim 1, wherein the component (b) is inorganic fine particles. 2. The method of forming a bank pattern according to claim 1, wherein the component (b) is fine particles containing a coloring agent. When the component (b) is inorganic fine particles, it has an average temporary particle size of 5 nm to 100 nm, and when it is organic fine particles, it has an average particle size of 5 nm to 1000 nm. A method for forming a bank pattern according to any one of the items. 5. The method of forming a bank pattern according to claim 1, wherein the first photosensitive resin composition satisfies at least one of (Z1) to (Z4) below.
(Z1): further containing a cross-linking agent as component (E);
(Z2): The alkali-soluble resin having an amide group of component (A) further has a self-crosslinking group or at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group and an amino group. further having reactive groups;
(Z3): a photoradical generator in which component (D) is (D-2), and further contains a compound having two or more ethylenic double bonds as component (F);
(Z4): A photoacid generator in which the (D) component is (D-3), and further, as the (G) component, two or more functional groups that form a covalent bond with the acid generated from the (D) component. contains a compound that has 6. The method of forming a bank pattern according to claim 1, wherein the second photosensitive resin composition satisfies at least one of the following (z1) to (z4).
(z1): further containing a cross-linking agent as component (e);
(z2): The alkali-soluble resin of component (a) further has a self-crosslinking group or a group that reacts with at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group and an amino group. further have;
(z3): a photoradical generator in which component (d) is (d-2), and further contains a compound having two or more ethylenic double bonds as component (f);
(z4): a photoacid generator in which the (d) component is (d-3), and as the (g) component, two or more functional groups that form a covalent bond with the acid generated from the (d) component. contains a compound that has 5. The method of forming a bank pattern according to any one of claims 1 to 4, wherein the component (D) and/or (d) is a quinonediazide compound. 6. The method of forming a bank pattern according to claim 5, wherein component (D) is a quinonediazide compound and further satisfies either of (Z1) and/or (Z2). 7. The method of forming a bank pattern according to claim 6, wherein component (d) is a quinonediazide compound and further satisfies either of (z1) and/or (z2). 9. The method of forming a bank pattern according to claim 8, wherein component (D) is diazonaphthoquinone. 10. The method of forming a bank pattern according to claim 9, wherein the component (d) is diazonaphthoquinone. 12. The method of forming a bank pattern according to any one of claims 1 to 11, wherein the second photosensitive resin composition further contains the following component (h).
(h) component: a polymer having a liquid-repellent group (h1) 13. The method of forming a bank pattern according to claim 12, wherein the component (h) further comprises a polymer having the following (h2).
(h2): at least one group selected from an N-alkoxymethylamide group, a blocked isocyanate group and a trialkoxysilyl group 14. The method of forming a bank pattern according to claim 12 or 13, wherein the component (h) is a polymer having the following (h3).
(h3): at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group and an amino group At least the liquid-repellent group (h1) of component (h) is selected from the group consisting of a fluoroalkyl group having 3 to 10 carbon atoms, a polyfluoroether group, a silyl ether group and a polysiloxane group represented by Formula 5 15. The method of forming a bank pattern according to any one of claims 12 to 14, which is a kind of group.
—(SiR ¹ R ² —O) _n —SiR ¹ R ² R ³ Formula 5
(where R ¹ and R ² independently represent a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group; R ³ represents hydrogen or an organic group having 1 to 10 carbon atoms; n is an integer of 1 to 200; represents.) 16. The method of forming a bank pattern according to any one of claims 12 to 15, wherein the polymer of component (h) is an acrylic polymer. 17. The method of forming a bank pattern according to claim 16, wherein the acrylic polymer of component (h) has a number average molecular weight of 2,000 to 100,000 in terms of polystyrene. 18. The bank pattern formation according to any one of claims 12 to 17, wherein component (h) accounts for 0.1 to 20 parts by mass in 100 parts by mass of component (a). Method. 12. The method of forming a bank pattern according to any one of claims 1 to 11, wherein the component (a) is a resin having a liquid-repellent group (h1) and does not contain the component (h). 20. The method of forming a bank pattern according to claim 19, wherein polymer units having a liquid-repellent group (h1) account for 5 to 30 parts by weight in 100 parts by weight of component (a). 21. The number average molecular weight of component (A) having an amide group and/or component (a) alkali-soluble resin is 2,000 to 50,000 in terms of polystyrene. A method for forming a bank pattern according to item 1. 22. The method of forming a bank pattern according to any one of claims 1 to 21, wherein component (b) is contained in an amount of 5 to 500 parts by mass with respect to 100 parts by mass of component (a). . 23. The bank pattern formation according to any one of claims 5 to 22, wherein component (E) is 1 part by mass to 50 parts by mass with respect to 100 parts by mass of component (A). Method. 24. The method of forming a bank pattern according to claim 1, wherein the other layer is an organic electroluminescent hole injection layer. A bank pattern having banks and regions partitioned by the banks on a substrate,
The bank comprises, from the substrate side, at least: a substrate; an underlayer film made of a first photosensitive resin composition containing components (A), (C) and (D) below; and a resist film made of a second photosensitive resin composition containing components (b), (c) and (d), and the regions defined by the banks are the underlayer film and the resist film bank pattern without
(A) component: an alkali-soluble resin having an amide group (the amide group is derived from at least one monomer selected from acrylamide and methacrylamide);
(C) component: solvent,
(D) component: photosensitizer,
(a) component: alkali-soluble resin,
(b) component: fine particles,
(c) component: solvent,
(d) component: photosensitizer A display element having the bank pattern according to claim 25. A display element having the bank pattern according to claim 25 as an image forming partition.

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