JP7709129B2 - Method for forming a bank pattern - 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. This method for forming a bank pattern of a cured film using a photosensitive resin composition is particularly suitable as a method for forming an interlayer insulating film in a liquid crystal display or an EL display, or a light-shielding wall or partition wall compatible with the inkjet method.

In recent years, full-color display substrate manufacturing techniques using inkjet have been actively studied in the manufacturing process of display elements such as thin film transistor (TFT) type liquid crystal display elements and organic electroluminescent (EL) elements. For example, in relation to the manufacture of color filters in liquid crystal display elements, in contrast to the conventional printing method, electrodeposition method, dyeing method or pigment dispersion method, a color filter and its manufacturing method (Patent Document 1) have been proposed in which a partition (hereinafter referred to as a bank) that defines a patterned pixel is formed in advance with a light-blocking photosensitive resin layer, and ink droplets are dropped into the area surrounded by this bank. In addition, in the case of organic EL display elements, a method has been proposed in which a bank is formed in advance, and ink that becomes a light-emitting layer is similarly dropped to manufacture the organic EL display element (Patent Document 2).
However, when using the inkjet method to drop ink droplets into an area surrounded by a bank, in order to prevent the ink droplets from spilling over the bank into adjacent pixels, the substrate must be made ink-philic (hydrophilic) and the surface of the bank must be made water-repellent.

To achieve the above objective, it has been proposed that successive plasma (ozone) treatments such as oxygen gas plasma treatment and fluorine gas plasma treatment can be used to make the substrate hydrophilic and the bank water-repellent (Patent Document 3), but the process is complicated. In addition, a proposal has been made to blend a fluorine-based surfactant or a fluorine-based polymer into a photosensitive organic thin film (Patent Document 4), but not only are there many points to consider, including compatibility and the amount of addition, including not only photosensitivity but also coating properties, and the UV ozone treatment during the hydrophilic treatment of the substrate reduces the water-repellency of the surface, making it impractical.

To achieve the above objective, a method has been proposed in which a layer containing a hydrophilic compound is provided under a liquid-repellent bank material, and this is developed and removed together with the upper layer of bank material, thereby preventing contamination of the bank openings, which should be lyophilic, by the components of the bank material (Patent Documents 5 to 7). However, this method has problems in that the lower layer is highly hydrophilic, making it prone to moisture absorption, and also makes it prone to pattern peeling during the development process.

To achieve the above-mentioned objective, a method has been proposed in which an organic layer is provided under a liquid-repellent bank material, and after forming a pattern with the upper layer of the bank material, the lower layer is removed by a dry etching process to improve the lyophilicity of the bank opening (Patent Document 8). However, this method has the problem of being complicated.

Patent Documents 9 and 10 have also proposed methods for forming patterns by performing one exposure step and one development step on two stacked organic layers. However, neither of these methods was aimed at forming a bank pattern with liquid repellency. In addition, in the method of Patent Document 9, the lower organic layer does not have photosensitivity, so precise process control was required to control the dimensions of the pattern. In the method of Patent Document 10, a heat treatment must be performed after the exposure step, making the process complicated.

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

The present invention provides a method for forming a bank pattern that is less likely to leave residues of components of the liquid-repellent resist material in areas other than the bank, even when using a liquid-repellent bank that is easy to process and advantageous in terms of production costs.

The present inventors have found that a first photosensitive resin composition containing an alkali-soluble resin having an amide group is applied directly or through another layer onto a substrate to provide an underlayer film, a second photosensitive resin composition containing a polymer that is a liquid-repellent component is applied onto the underlayer film to provide a resist film, and the resist film is exposed and developed to form a bank. In this development process, the underlayer film in the non-bank portion is removed together with the resist film in the non-bank portion, thereby reducing the amount of resist film residue containing the liquid-repellent component on the substrate and efficiently imparting water repellency and liquid repellency to the film surface while maintaining the lyophilicity of the openings, and thus completed the present invention.
Here, the area on the substrate where the banks are located is referred to as a bank portion, and the area other than the banks is referred to as a non-bank portion.

That is, the present invention relates to the following.
1. A method for forming a bank and an area defined by the bank on a substrate, the method comprising the steps of: forming a bank pattern for forming an organic thin film in the area defined by the bank, the method comprising the steps of:
an underlayer film forming step of applying a first photosensitive resin composition containing the following components (A), (C) and (D) directly onto a substrate or via another layer to provide an underlayer film;
a resist film forming step of coating a second photosensitive resin composition containing the following components (a), (b), (c) and (d) on the underlayer film to provide a resist film;
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 development process.
Component (A): an alkali-soluble resin having an amide group,
(C) component: solvent,
(D) component: photosensitizer,
Component (a): an alkali-soluble resin,
Component (b): a polymer having a liquid repellent group (b1),
(c) component: solvent,
(d) Component: Photosensitizer.
2. The method for forming a bank pattern according to the above item 1, wherein the first photosensitive resin composition satisfies at least one of the following (Z1) to (Z4):
(Z1): Further containing a crosslinking agent as the component (E);
(Z2): The alkali-soluble resin having an amide group of the component (A) further has a self-crosslinking group, or further has a group reactive with at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, and an amino group;
(Z3): A photoradical generator in which the component (D) is (D-2) and further contains a compound having two or more ethylenic double bonds as the component (F);
(Z4): A photoacid generator in which the component (D) is (D-3), and which further contains, as the component (G), a compound having two or more functional groups that form a covalent bond with the acid generated from (D-3).
3. The method for forming a bank pattern according to 1 or 2 above, wherein the second photosensitive resin composition satisfies at least one of the following (z1) to (z4):
(z1): Further containing a crosslinking agent which is the component (e);
(z2): The alkali-soluble resin of the component (a) further has a self-crosslinking group, or further has a group reactive with at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, and an amino group;
(z3): A photoradical generator in which the component (d) is (d-2) and further contains a compound having two or more ethylenic double bonds as the component (f);
(z4): A photoacid generator in which the component (d) is (d-3), and which further contains, as the component (g), a compound having two or more functional groups that form a covalent bond with the acid generated from (d-3).
4. The method for forming a bank pattern according to any one of the above 1 to 3, wherein the component (D) and/or (d) is a quinone diazide compound.
5. The method for forming a bank pattern as described in the above 2, wherein the component (D) is a quinone diazide compound and further satisfies either (Z1) or (Z2).
6. The method for forming a bank pattern as described in the above 3, wherein the component (d) is a quinone diazide compound and further satisfies either (z1) or (z2).
7. The method for forming a bank pattern according to the above 5, wherein the component (D) is diazonaphthoquinone. 8. The method for forming a bank pattern according to the above 6, wherein the component (d) is diazonaphthoquinone. 9. The method for forming a bank pattern according to any one of the above 1 to 8, wherein the liquid repellent group (b1) is at least one group selected from a fluoroalkyl group having 3 to 10 carbon atoms, a polyfluoroether group, a silyl ether group, and a polysiloxane group represented by the following formula 4:
-(SiR ¹ R ² -O) _n -SiR ¹ R ² R ³ Formula 4
(wherein R ¹ and R ² independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group; R ³ represents a hydrogen atom or an organic group having 1 to 10 carbon atoms; and n represents an integer of 1 to 200.)
10. The method for forming a bank pattern according to any one of the above 1 to 9, wherein the number average molecular weight of the alkali-soluble resin having an amide group as component (A) and/or the alkali-soluble resin as component (a) is 2,000 to 50,000 in terms of polystyrene.
11. The method for forming a bank pattern according to any one of 2 to 10 above, wherein the component (E) is 1 part by mass to 50 parts by mass per 100 parts by mass of the component (A).
12. The method for forming a bank pattern according to any one of 1 to 11 above, characterized in that the composition contains 0.1 to 20 parts by mass of the component (b) per 100 parts by mass of the component (a).
13. The method for forming a bank pattern according to any one of the above 1 to 12, wherein the polymer of component (b) is an acrylic polymer.
14. The method for forming a bank pattern as described above in 13, wherein the acrylic polymer of component (b) has a number average molecular weight of 2,000 to 100,000 in terms of polystyrene.
15. The method for forming a bank pattern according to any one of items 3 to 14 above, wherein the amount of component (e) is 1 part by mass to 50 parts by mass per 100 parts by mass of the total of components (a) and (b).
16. The method for forming a bank pattern according to any one of the above items 1 to 15, wherein the component (b) is a polymer further comprising the following (b2):
(b2): At least one group selected from the group consisting of an N-alkoxymethylamide group, a blocked isocyanate group, and a trialkoxysilyl group.
17. The method for forming a bank pattern according to any one of the above 1 to 16, wherein the component (b) is a polymer further having the following (b3):
(b3): at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group, and an amino group.
18. The method for forming a bank pattern according to any one of the above 1 to 11, wherein the component (a) is a resin having a liquid repellent group (b1) and does not contain a component (b).
19. The method for forming a bank pattern according to the above item 18, characterized in that the polymerized unit having the liquid repellent group (b1) occupies 5 to 30 parts by mass in 100 parts by mass of the component (a).
20. The method for forming a bank pattern according to the above 18 or 19, wherein the component (e) is 1 part by mass to 50 parts by mass per 100 parts by mass of the component (a).
21. The method for forming a bank pattern according to any one of the above 1 to 20, wherein the other layer is an organic electroluminescent hole injection layer.
22. A cured film formed by the method for forming a bank pattern according to any one of 1 to 21 above.
23. A display device having the cured film according to 22 above.
24. A display device having the cured film according to 22 above as a partition for image formation.
25. A photosensitive resin composition for forming an underlayer film of a resist film, comprising the following components (A), (C) and (D):
Component (A): an alkali-soluble resin having an amide group,
(C) component: solvent,
Component (D): Photosensitizer.

According to the method for forming a bank pattern of the present invention, even if a liquid-repellent bank is used, which is easy to process and advantageous in terms of production costs, it is possible to form a bank pattern that improves the liquid affinity of the substrate surface by suppressing the residue of components of the liquid-repellent resist material on the substrate surface in the non-bank portion. In other words, it is possible to achieve both the liquid repellency of the bank and the liquid affinity of the non-bank portion, and a uniform organic thin film can be formed within the area partitioned by the bank.

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

The method for forming a bank pattern according to the present invention will now be described in detail.
The method for forming a bank pattern of the present invention is a method for forming a bank and an area defined by the bank on a substrate, the method comprising the steps of:
an underlayer film forming step of applying a first photosensitive resin composition containing the following components (A), (C) and (D) directly onto a substrate or via another layer to provide an underlayer film;
a resist film forming step of coating a second photosensitive resin composition containing the following components (a), (b), (c) and (d) on the underlayer film to provide a resist film;
The resist film is exposed to light and developed to form banks, and during the development process the underlying film in the non-bank portions is removed together with the resist film in the non-bank portions to form a bank.
Component (A): an alkali-soluble resin having an amide group; Component (C): a solvent; Component (D): a photosensitizer; Component (a): an alkali-soluble resin; Component (b): a polymer having a liquid-repellent group (b1); Component (c): a solvent; Component (d): a photosensitizer

In the second photosensitive resin composition of the present invention, the component (b) is preferably a polymer further having the following (b2):
(b2): At least one group selected from the group consisting of an N-alkoxymethylamide group, a blocked isocyanate group, and a trialkoxysilyl group.
In the second photosensitive resin composition of the present invention, the component (b) is preferably a polymer further having the following (b3):
(b3): at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group, and an amino group.

It is preferable that the first photosensitive resin composition of the present invention further satisfies at least one of the following (Z1) to (Z4).
(Z1): Further contains a crosslinking agent which is the component (E);
(Z2): The alkali-soluble resin having an amide group of the component (A) further has a self-crosslinking group, or further has a group reactive with at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, and an amino group;
(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 component (D) is (D-3), and which further contains, as the component (G), a compound having two or more functional groups that form a covalent bond with the acid generated from the component (D-3).

It is preferable that the second photosensitive resin composition of the present invention further satisfies at least one of the following (z1) to (z4).
(z1): Further containing a crosslinking agent which is the component (e);
(z2): The alkali-soluble resin of the component (a) further has a self-crosslinking group, or further has a group reactive with at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, and an amino group;
(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 component (d) is (d-3), and further contains, as the component (g), a compound having two or more functional groups that form a covalent bond with the acid generated from the component (d-3).

The photosensitive resin composition of the present invention is preferably a positive-type photosensitive resin composition in which component (D) and/or (d) is a quinone diazide compound.

The method for forming a bank pattern of the present invention will be described below with reference to FIG. 1.

<Lower film formation process>
In the manufacturing method of the present invention, first, a first photosensitive resin composition comprising a monomer having an amide group and a monomer having an alkali-soluble group, which will be described later, is applied to a substrate 11 directly or through another layer, and then prebaked to provide an underlayer film 12 that is not liquid repellent.

The components of the undercoat film are explained in detail below.

<Component (A)>
The component (A) of the present invention is an alkali-soluble resin having an amide group. The amide group forms hydrogen bonds within or between molecules, and when the upper resist film described below is applied, the resin exhibits resistance to the solvent, and the upper 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 to impart alkali solubility, and examples of the alkali-soluble group include a phenolic hydroxyl group, a carboxyl group, an acid anhydride group, an imide group, a sulfonyl group, a phosphoric acid group, a boronic acid group, an active methylene group, and an active methine group. The phenolic hydroxyl group and the carboxyl group are alkali-soluble groups, and are also heat-reactive sites (sites that can form a crosslinked structure with the crosslinking agent of component (E)) as described below.
In addition, the component (A) is not particularly limited in terms of other structure or functional group contained therein, so long as it is an alkali-soluble resin having the above-mentioned amide group. For example, in the case where the component (A) contains a compound having two or more functional groups that form a covalent bond with an acid (G) described later, the component (A) may not have a reactive site with the component (G), and in the case where the component (A) has a reactive site with the component (G), the reactive site is not particularly limited as long as it is a group that can form a covalent bond with the component (G) by the action of an acid, or a group that can form a covalent bond with the component (G) by heating.

The term "active methylene group" as used herein refers to a methylene group ( _-CH2- ) which has a carbonyl group adjacent to it and is reactive to nucleophiles. The term "active methine group" as used herein refers to an active methylene group which has a structure in which one hydrogen atom of the methylene group is substituted with an alkyl group and is reactive to nucleophiles.

Among the active methylene groups and active methine groups, the active methylene groups are preferred, and the 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), examples of the alkyl group represented by R include alkyl groups having 1 to 20 carbon atoms, and alkyl groups having 1 to 5 carbon atoms are preferred.
Examples of such an alkyl group include a methyl group, an ethyl group, an n-propyl group, and an i-propyl group.
Of these, a methyl group, an ethyl group, an n-propyl group, etc. are preferred.

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

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

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

The alkali-soluble resin of component (A) above may be an alkali-soluble resin having such a structure, and there are no particular limitations on the main chain skeleton and the type of side chain of the polymer constituting the resin.

However, the number average molecular weight of the alkali-soluble resin of component (A) is within the range of 2,000 to 50,000. If the number average molecular weight is too high, exceeding 50,000, development residues are likely to be generated and sensitivity will decrease significantly, while if the number average molecular weight is too low, below 2,000, a considerable amount of film loss will occur in the exposed areas during development, which may result in insufficient curing.

Examples of the alkali-soluble resin of component (A) include acrylic resins, polyhydroxystyrene resins, polyimide precursors, polyimides, etc. Among these, acrylic resins (acrylic polymers) are preferred.

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

That is, the above-mentioned specific copolymer is a copolymer formed by using, as essential constituent units, a monomer having an amide group, a monomer exhibiting alkali solubility, i.e., a monomer having at least one group selected from the group consisting of a carboxyl group and a phenolic hydroxyl group as a suitable alkali soluble group, and, if desired, at least one monomer selected from the group of monomers copolymerizable with these monomers, and has a number average molecular weight of 2,000 to 50,000. If the number average molecular weight is more than 50,000, residues may be generated.
The monomer having an amide group may also have an alkali-soluble group.

Examples of the monomer having an amide group include acrylamide, methacrylamide, N-methylacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, N-phenylmethacrylamide, N-phenylacrylamide, 4-hydroxyphenylmethacrylamide, 4-hydroxyphenylacrylamide, etc., which can be used alone or in combination of two or more. Among them, methacrylamide is preferred.

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

Specific examples of the monomer are given below, but the monomer is 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, and N-(carboxyphenyl)acrylamide.

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

In the production of the alkali-soluble resin (specific copolymer) of component (A), the ratio of monomers that exhibit alkali solubility, for example, the ratio of monomers having at least one group selected from the group consisting of carboxyl groups and phenolic hydroxyl groups, is preferably 5% by mass or more, more preferably 10% by mass or more, of all monomers used in the production of the alkali-soluble resin (specific copolymer) of component (A). If the monomers that exhibit alkali solubility (monomers having at least one group selected from the group consisting of carboxyl groups and phenolic hydroxyl groups) are less than 5% by mass, the alkali-soluble resin (acrylic polymer) will have insufficient alkali solubility.

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

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

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, and 5-acryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone.

When a monomer having a hydroxyalkyl group and a polymerizable unsaturated group is used in the production of the alkali-soluble resin (specific copolymer) of component (A), the ratio of the monomer to all monomers used in the production of the specific copolymer is preferably 5% to 60% by mass, more preferably 10% to 50% by mass, and most preferably 20% to 40% by mass. If 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 it is 60% by mass or more, the proportion of alkali-soluble groups in component (A) may be insufficient, and characteristics such as developability may be deteriorated.

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

Examples of N-substituted maleimide compounds include N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide. From the viewpoint of transparency, compounds without aromatic rings are preferred, and from the viewpoints of developability, transparency, and heat resistance, compounds with alicyclic skeletons are more preferred, and among these, cyclohexylmaleimide is the most preferred.

When N-substituted maleimide is used in the production of the alkali-soluble resin (specific copolymer) of component (A), the ratio of the N-substituted maleimide to all monomers used in the production of the specific copolymer is preferably 5 to 60% by mass, more preferably 10 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 solvents 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 is preferably a copolymer further having a self-crosslinking group or further having a group (hereinafter also referred to as a crosslinking 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. For example, the requirement (Z2) can be satisfied by introducing a repeating unit having at least one group selected from the group consisting of the self-crosslinking group and the crosslinking group into the alkali-soluble resin (A).

The above-mentioned self-crosslinking groups include N-alkoxymethyl groups, N-hydroxymethyl groups, alkoxysilyl groups, epoxy groups, oxetanyl groups, vinyl groups, and blocked isocyanate groups.

Examples of the crosslinkable group include an N-alkoxymethyl group, an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, a vinyl group, and a blocked isocyanate group.

When such self-crosslinking groups or crosslinking groups are contained in the alkali-soluble resin of component (A), the content of the self-crosslinking groups or units having crosslinking groups is preferably 10% to 70% by mass, and particularly preferably 20% to 60% by mass, based on the total of all repeating units in the resin of component (A).

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

Examples of monomers that are radically polymerizable and have an N-alkoxymethyl group include N-butoxymethylacrylamide, N-isobutoxymethylacrylamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, and N-methylolacrylamide.

Examples of monomers that are radically polymerizable and further have an N-hydroxymethyl group include N-hydroxymethylacrylamide and N-hydroxymethylmethacrylamide.

Examples of monomers that are radically polymerizable and further have an alkoxysilyl group include 3-acryloyloxytrimethoxysilane, 3-acryloyloxytriethoxysilane, 3-methacryloyloxytrimethoxysilane, and 3-methacryloyloxytriethoxysilane.

Examples of monomers having radical polymerization properties and further having an epoxy group include glycidyl acrylate, glycidyl methacrylate, α-ethyl glycidyl acrylate, α-n-propyl glycidyl acrylate, α-n-butyl glycidyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 3,4-epoxycyclohexyl methacrylate, 6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl methacrylate, α-ethyl acrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, etc. 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. are preferably used. These can be used alone or in combination.

Examples of the monomer having radical polymerization properties and further 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-(acryloyloxymethyl)-4-trifluoromethyloxetane are preferred, and 3-(methacryloyloxymethyl)-3-ethyl-oxetane, 3-(acryloyloxymethyl)-3-ethyl-oxetane, and the like are preferably used.

Examples of monomers that are radically polymerizable and further have a vinyl group include 2-(2-vinyloxyethoxy)ethyl acrylate and 2-(2-vinyloxyethoxy)ethyl methacrylate.

Examples of monomers that are radically polymerizable and further have a blocked isocyanate group include 2-(0-(1'-methylpropylideneamino)carboxyamino)ethyl methacrylate and 2-(3,5-dimethylpyrazolyl)carbonylamino)ethyl methacrylate.

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

In the present invention, the alkali-soluble resin (specific copolymer, for example, acrylic polymer) of the component (A) may be a copolymer formed using monomers other than the above-mentioned monomers (hereinafter referred to as other monomers) as structural units. Specifically, the other monomers may be those that are copolymerizable with at least one selected from the group consisting of the above-mentioned monomers having a carboxyl group and monomers having a phenolic hydroxy group, and are not particularly limited as long as they do not impair the properties of the component (A). Specific examples of such monomers include acrylic acid ester compounds, methacrylic acid ester compounds, N-substituted acrylamide compounds, maleimides, acrylonitrile, styrene compounds, and vinyl compounds.
Specific examples of the other monomers are given below, but the present invention is not limited thereto.

Examples of the acrylic acid ester compounds 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, methoxytriethylene glycol ... Examples of such acrylates include oxyethyl acrylate, 2-aminoethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl 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 monoacrylate, caprolactone 2-(acryloyloxy)ethyl ester, and poly(ethylene glycol) ethyl ether acrylate.

Examples of the methacrylic acid ester compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, glycidyl methacrylate, phenoxyethyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol ... methacrylate, 2-ethoxyethyl methacrylate, 2-aminomethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl 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, and poly(ethylene glycol) ethyl ether methacrylate.

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

The styrene compound includes styrenes that do not have a hydroxy group, such as styrene, α-methylstyrene, chlorostyrene, and bromostyrene.

Examples of the vinyl compounds include methyl vinyl ether, benzyl vinyl ether, cyclohexyl vinyl ether, vinyl naphthalene, vinyl anthracene, vinyl carbazole, 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) which is component (A), the ratio of the above 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, based on all the monomers used in the production of the specific copolymer. If the ratio exceeds 80% by mass, the amount of essential components (essential monomers constituting component (A)) will be relatively reduced, making it difficult to fully 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, but for example, a monomer having a group selected from an amide group and a carboxyl group and at least one group selected from an alkali-soluble group such as a carboxyl group, a phenolic hydroxyl group, etc., and optionally a monomer having a hydroxyalkyl group, an N-substituted maleimide compound, and optionally a monomer having at least one group selected from a self-crosslinking group such as an N-alkoxymethyl group, an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, an oxetanyl group, a vinyl group, and a blocked isocyanate group, and a crosslinking group such as an N-alkoxymethyl group, an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, a vinyl group, and a blocked isocyanate group, and optionally other copolymerizable monomers and optionally a polymerization initiator, etc., are polymerized in a solvent at a temperature of 50 to 110 ° C. to obtain the resin. In this case, 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 include the solvents described below for component (C).

The alkali-soluble resin (specific copolymer) of component (A) thus obtained is usually in the form of a solution dissolved in a solvent. In the present invention, the solution of the alkali-soluble resin (specific copolymer) of component (A) obtained may be used as 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 can be reprecipitated by adding diethyl ether, water, etc. under stirring, and the resulting precipitate can be filtered and washed, and then dried at room temperature or by heating under normal pressure or reduced pressure to obtain a powder of the specific copolymer. By such an operation, the polymerization initiator and unreacted monomers coexisting with the specific copolymer can be removed, and as a result, a powder of the purified specific copolymer can be obtained. If the specific copolymer cannot be sufficiently purified by one operation, the obtained powder can be redissolved in a solvent and the above operation can be repeated.
In the present invention, the powder of the specific copolymer may be used as it is as the alkali-soluble resin of component (A), or the powder may be redissolved in component (C) described below and used in the form of a solution.

In addition, 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 also be used, and there are no particular limitations on the type of these that can be used as long as they are alkali-soluble.

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

The (a) tetracarboxylic acid dianhydride compound is not particularly limited, and specific examples thereof include aromatic tetracarboxylic acids such as pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 3,3',4,4'-benzophenonetetracarboxylic acid dianhydride, 3,3',4,4'-diphenylethertetracarboxylic acid dianhydride, and 3,3',4,4'-diphenylsulfonetetracarboxylic acid dianhydride; 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2-dimethyl-1,2,3,4- Examples of the tetracarboxylic acid dianhydride include alicyclic tetracarboxylic acid dianhydrides such as cyclobutane tetracarboxylic acid dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,2,3,4-cyclopentane tetracarboxylic acid dianhydride, 1,2,3,4-cyclohexane tetracarboxylic acid dianhydride, and 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid dianhydride; and aliphatic tetracarboxylic acid dianhydrides such as 1,2,3,4-butane tetracarboxylic acid dianhydride.
These may be used alone or in combination of two or more compounds.

The diamine compound (j) is not particularly limited, and examples thereof include 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, 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-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, diamine compounds having a carboxyl group such as bis[4-(4-amino-3-carboxyphenoxy)phenyl]benzene, bis[4-(4-amino-3-carboxyphenoxy)phenyl]sulfone, bis[4-(4-amino-3-carboxyphenoxy)phenyl]propane, and 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, and 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 phenyl, 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)benzene, diamine compounds having a phenolic hydroxy group, such as 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- diamine compounds having a thiophenol group, such as 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, and 4,4'-diamino-3,3'-dimethylbiphenyl-6,6'-disulfonic acid. In addition, p-phenylenediamine, m-phenylenediamine, 4,4'-methylene-bis(2,6-ethylaniline), 4,4'-methylene-bis(2-isopropyl-6-methylaniline), 4,4'-methylene-bis(2,6-diisopropylaniline), 2,4,6-trimethyl-1,3-phenylenediamine, 2,3,5,6-tetramethyl-1,4-phenylenediamine, o-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'-dimethyldicyclohexyl Examples of the diamine compounds include 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-tolyl)hexafluoropropane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, and 2,2'-bis(trifluoromethyl)benzidine.
These may be used alone or in combination of two or more compounds.

When the polyamic acid used in the present invention is produced from (i) a tetracarboxylic dianhydride compound and (j) a diamine compound, the compounding ratio of the two compounds, i.e., the total number of moles of (j) diamine compound/the total number of moles of (i) tetracarboxylic dianhydride compound, is preferably 0.7 to 1.2. As with a normal polycondensation reaction, the closer this molar ratio is to 1, the greater the degree of polymerization of the polyamic acid produced, and the greater the molecular weight.

In addition, when polymerization is carried out using an excess of a diamine compound, the terminal amino groups of the remaining polyamic acid can be protected by reacting them with a carboxylic acid anhydride.
Examples of such carboxylic acid anhydrides include phthalic anhydride, trimellitic anhydride, maleic anhydride, naphthalic anhydride, hydrogenated phthalic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, itaconic anhydride, and tetrahydrophthalic anhydride.

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 any temperature range of −20 to 150° C., preferably −5 to 100° C. To obtain a high molecular weight polyamic acid, the reaction temperature is appropriately selected from the range of 5° C. to 40° C. and the reaction time is appropriately selected from the range of 1 to 48 hours. To obtain a low molecular weight, partially imidized polyamic acid with high storage stability, it is more preferable to select the reaction temperature from 40° C. to 90° C. and the reaction time from 10 hours or more.
When the terminal amino group is protected with an acid anhydride, the reaction temperature can be selected from the range of -20 to 150°C, preferably -5 to 100°C.

The reaction between the diamine compound and the tetracarboxylic dianhydride compound can be carried out in a solvent. Solvents that can be used in this reaction include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, N-methylcaprolactam, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, m-cresol, γ-butyrolactone, ethyl acetate, butyl acetate, ethyl lactate, methyl 3-methoxypropionate, methyl 2-methoxypropionate, ethyl 3-methoxypropionate, ethyl 2-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 2-ethoxypropionate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and 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, etc. These may be used alone or in combination. Furthermore, even if a solvent does not dissolve polyamic acid, it may be mixed with the above solvent and used as long as the polyamic acid produced by the polymerization reaction does not precipitate.

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

In addition, any polyimide can be used as component (A). The polyimide used in the present invention is a polyimide precursor such as the polyamic acid that has been chemically or thermally imidized to 50% or more.

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

Such a polyimide can be obtained by synthesizing a polyimide precursor such as the above-mentioned polyamic acid, and then carrying out chemical imidization or thermal imidization.
A typical method for chemical imidization is to add excess acetic anhydride and pyridine to a polyimide precursor solution and react them at room temperature to 100° C. A typical method for thermal imidization is to heat a polyimide precursor solution at a temperature of 180° C. to 250° C. while dehydrating it.

In addition, phenol novolac resin can also be used as the alkali-soluble resin of component (A).

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

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

<(C) component>
The component (C) used in the present invention serves as a solvent that dissolves the component (A) and, if necessary, the components (D), (E), (F), and (G) described below, as well as other additives that are added as desired, and there are no particular limitations on the type or structure of the solvent as long as it is a solvent that has such dissolving ability.

Examples of such (C) components 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, 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 N-methylpyrrolidone.

These solvents may be used alone or in combination of two or more.
Of these components (C), 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. are preferred from the viewpoint of good film-forming properties and high safety, and propylene glycol monomethyl ether, propylene glycol propyl ether, ethyl lactate, butyl lactate, etc. are particularly preferred from the viewpoint of the solubility of component (A). These solvents are generally used as solvents for photoresist materials.

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

The 1,2-quinonediazide compound (D-1) is a compound having either a hydroxy group or an amino group, or both a hydroxy group and an amino group, in which preferably 10 mol % to 100 mol %, particularly preferably 20 mol % to 95 mol %, of these hydroxy groups or amino groups (in the case of having both a hydroxy group and an amino group, the total amount of the groups) is esterified or amidated with 1,2-quinonediazide sulfonic acid.
Examples of the 1,2-quinonediazide sulfonic acid include 1,2-naphthoquinone-2-diazide-5-sulfonic acid, 1,2-naphthoquinone-2-diazide-4-sulfonic acid, and 1,2-benzoquinone-2-diazide-4-sulfonic acid. In the reaction with the compound having either or both of a hydroxy group and an amino group, a chloride of the 1,2-quinonediazide sulfonic acid can be used.
As the 1,2-quinonediazide compound (D-1), diazonaphthoquinone can be used.

Examples of compounds having a hydroxyl 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 [N] phenol compounds such as bisphenol, 2,4-dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2',3,4,4'-pentahydroxybenzophenone, and 2,5-bis(2-hydroxy-5-methylbenzyl)methyl; and aliphatic alcohols such as ethanol, 2-propanol, 4-butanol, cyclohexanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 2-methoxyethanol, 2-butoxyethanol, 2-methoxypropanol, 2-butoxypropanol, ethyl lactate, and butyl lactate.

Examples of compounds containing the amino group include anilines such as aniline, o-toluidine, m-toluidine, p-toluidine, 4-aminodiphenylmethane, 4-aminodiphenyl, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminophenylmethane, and 4,4'-diaminodiphenylether, and aminocyclohexane.

Furthermore, examples of compounds containing both hydroxyl and amino groups include aminophenols such as 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, and 2,2-bis(4-amino-3-carboxy-5-hydroxyphenyl)hexafluoropropane, as well as alkanolamines such as 2-aminoethanol, 3-aminopropanol, and 4-aminocyclohexanol.

These 1,2-quinone diazide 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 quinone diazide group as component (D-1) is preferably 5 to 100 parts by mass, more preferably 8 to 50 parts by mass, and even more preferably 10 to 40 parts by mass, relative to 100 parts by mass of component (A). If it is less than 5 parts by mass, the difference in dissolution rate in the developer between the exposed and unexposed parts of the positive photosensitive resin composition becomes small, and patterning by development may be difficult. If it exceeds 100 parts by mass, the 1,2-quinone diazide compound may not be sufficiently decomposed by short-term exposure, resulting in a decrease in sensitivity, or the component (D-1) may absorb light, resulting in a decrease in transparency of the cured film.

There are no particular limitations on the photoradical generator (D-2) as long as it generates radicals upon exposure to light. Specific examples include aromatic ketones such as benzophenone, Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-ethylanthraquinone, and phenanthrene; benzoin ethers such as benzoin methyl ether, benzoin ethyl ether, and 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-benzo[b]phenylimid ... halomethyl oxadiazole compounds such as 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5-(p-cyanostyryl)-1,3,4-oxadiazole, and 2-trichloromethyl-5-(p-methoxystyryl)-1,3,4-oxadiazole; styryl-S-triazine, 2,4-bis(trichloromethyl)-6-(1-p-dimethylaminophenyl-1,3-butadienyl)-S-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl-S-triazine, 2-(naphth-1-yl)-4,6-bis-trichloromethyl-S-triazine, 2-(4-ethoxy-naphth-1-yl)-4,6-bis-trichloromethyl-S-triazine, 2-(4-butoxy halomethyl-S-triazine compounds such as 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-dimethylaminobenzoate 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-mentioned 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 (all manufactured by BASF), KAYACURE DETX-S, KAYACURE CTX, KAYACURE BMS, KAYACURE 2-EAQ (all 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 (all manufactured by Midori Kagaku Co., Ltd.), and the like.
These photoradical generators can be used alone or in combination of two or more kinds.

When the first photosensitive resin composition of the present invention contains the component (D-2), the content is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, and particularly preferably 1 to 15 parts by mass, per 100 parts by mass of the component (A). If this ratio is too small, the exposed areas may not be cured sufficiently, and pattern formation may not be possible, or even if it is possible, the resulting film may be unreliable. If this ratio is too large, the transmittance of the coating film may decrease, or development problems may occur in the unexposed areas.

The photoacid generator (D-3) is not particularly limited as long as it is a compound that generates an acid by photodecomposition when irradiated with ultraviolet light. Examples of acids that are generated when the photoacid generator is photodecomposed include sulfonic acids such as hydrochloric acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentanesulfonic acid, octane sulfonic 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-ethylbenzenesulfonic acid, 1H,1H,2H,2H-perfluorooctanesulfonic acid, perfluoro(2-ethoxyethane)sulfonic acid, pentafluoroethanesulfonic acid, nonafluorobutane-1-sulfonic acid, and dodecylbenzenesulfonic acid, or hydrates or salts thereof.

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, acetophenone derivative compounds, and cyano group-containing oxime sulfonate compounds. Any photoacid generator that has been known or has been used in the past can be applied to the present invention without any particular limitation. In the present invention, the photoacid generator of component (D) 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 the component (D-3), the content is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 8 parts by mass, per 100 parts by mass of the component (A). By making the content of the component (D-3) 0.01 parts by mass or more, sufficient thermosetting properties and solvent resistance can be imparted. However, if the content is more than 20 parts by mass, unexposed areas may not be developed properly, and the storage stability of the composition may decrease.

<(E) component>
The component (E) is a crosslinking 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 thermally reactive site (e.g., carboxyl group and/or phenolic hydroxy group) of the component (A). Specific examples are given below, but are not limited to these. The thermal crosslinking agent is preferably selected from, for example, (E1) a crosslinking compound having two or more substituents selected from an alkoxymethyl group and a hydroxymethyl group, or (E2) a crosslinking compound represented by the following formula (1). These crosslinking agents can be used alone or in combination of two or more.

When the crosslinkable compound (E1) having two or more substituents selected from alkoxymethyl groups and hydroxymethyl groups is exposed to high temperatures during thermal curing, the crosslinking reaction proceeds by a dehydration condensation reaction. Examples of such compounds include compounds such as alkoxymethylated glycoluril, alkoxymethylated benzoguanamine, and alkoxymethylated melamine, as well as phenoplast-based 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, and 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazolinone. Commercially available products include glycoluril compounds manufactured by Mitsui Cytec Co., Ltd. (product names: Cymel (registered trademark) 1170, Powderlink (registered trademark) 1174), methylated urea resin (product name: UFR (registered trademark) 65), butylated urea resin (product names: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), and urea/formaldehyde resins manufactured by DIC Corporation (high condensation type, product names: Beckamin (registered trademark) J-300S, P-955, N).

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

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

It may also be a compound obtained by condensing a melamine compound, a urea compound, a glycoluril compound, and a benzoguanamine compound in which the hydrogen atom of the amino group is substituted with a methylol group or an alkoxymethyl group. For example, there may be mentioned high molecular weight compounds produced from melamine compounds and benzoguanamine compounds described in U.S. Pat. No. 6,323,310. Commercially available products of the melamine compounds include Cymel (registered trademark) 303 (manufactured by Mitsui Cytec Co., Ltd.), and commercially available products of the benzoguanamine compounds include Cymel (registered trademark) 1123 (manufactured by Mitsui Cytec Co., Ltd.).

Specific examples of the phenoplast-based 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-methylethylidene)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(hydroxmethyl)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. These are also available as commercially available products, and specific examples thereof include 26DMPC, 46DMOC, DM-BIPC-F, DM-BIOC-F, TM-BIP-A, BISA-F, BI25X-DF, and BI25X-TPA (all manufactured by Asahi Organic Chemicals Co., Ltd.).

Furthermore, as component (E1), polymers produced using acrylamide compounds or methacrylamide compounds substituted with hydroxymethyl groups or alkoxymethyl groups, such as N-hydroxymethylacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethylacrylamide, and N-butoxymethylmethacrylamide, can also be used.

Examples of such polymers include poly(N-butoxymethylacrylamide), copolymers of N-butoxymethylacrylamide and styrene, copolymers of N-hydroxymethylmethacrylamide and methyl methacrylate, copolymers of N-ethoxymethylmethacrylamide and benzyl methacrylate, and copolymers of N-butoxymethylacrylamide, benzyl methacrylate, and 2-hydroxypropyl methacrylate. The weight average molecular weight of such polymers is 1,000 to 50,000, preferably 1,500 to 20,000, and more preferably 2,000 to 10,000.

The first photosensitive resin composition of the present invention may contain, as the component (E2), a crosslinkable compound represented by the following formula (1).
(In the formula, k is an integer of 2 to 10, m is an integer of 0 to 4, and R ¹¹ represents an organic group having a valence of k.)

The component (E2) 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 the commercially available products shown below.

Commercially available products include Epolead GT-401, GT-403, GT-301, GT-302, Celloxide 2021, and Celloxide 3000 (trade names manufactured by Daicel Corporation), alicyclic epoxy resins such as Denacol EX-252 (trade name manufactured by Nagase ChemteX Corporation), CY175, CY177, and CY179 (all trade names manufactured by Huntsman Corporation), Araldite CY-182, CY-192, and CY-184 (all trade names manufactured by Huntsman Corporation), Epiclon 200 and 400 (all trade names manufactured by DIC Corporation), and Epicoat 871 and 872 (all trade names manufactured by Mitsubishi Chemical Corporation). Examples include ED-5661, ED-5662 (all trade names manufactured by Celanese Coatings Co., Ltd.). These crosslinkable compounds can be used alone or in combination of two or more types.

Of these, from the viewpoints of process resistance, such as heat resistance, solvent resistance, and long-term baking resistance, as well as transparency, compounds having a cyclohexene oxide structure and represented by formulas E2-1 and E2-2, Epolead GT-401, GT-403, GT-301, GT-302, Celloxide 2021, and Celloxide 3000 are preferred.

In addition, as component E, compounds other than those shown as components (E1) and (E2) that can form a crosslinked structure by thermal reaction with the thermally reactive sites of component (A) (for example, a carboxyl group and/or a phenolic hydroxy group) can also be used. Specific examples of the epoxy compounds include 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-hexanediol diglycidyl ether, glycerin 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; VESTANAT B1358/100, VESTAGON BF Examples of isocyanate compounds include Takenate (registered trademark) B-1540 (the above are isocyanurate-type modified polyisocyanates, manufactured by Degussa Japan Co., Ltd.), Takenate (registered trademark) B-882N, and Takenate (registered trademark) B-7075 (the above are isocyanurate-type modified polyisocyanates, manufactured by Mitsui Chemicals, Inc.).

Furthermore, as component E, a polymer having two or more structures capable of forming a cross-linked structure by thermal reaction with the thermally reactive sites (e.g., carboxyl groups and/or phenolic hydroxyl groups) of component (A) can be used. Specifically, for example, polymers produced using compounds having an epoxy group such as glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, and 3,4-epoxycyclohexylmethyl methacrylate; polymers produced using compounds having an alkoxysilyl group such as 3-methacryloxypropyltrimethoxysilane; compounds having an isocyanate group such as 2-isocyanatoethyl methacrylate (KarenzMOI [registered trademark], manufactured by Showa Denko K.K.), 2-isocyanatoethyl acrylate (KarenzAOI [registered trademark], manufactured by Showa Denko K.K.), or polymers produced using compounds having a blocked isocyanate group such as 2-(0-[1'-methylpropylideneamino]carboxyamino)ethyl methacrylate (KarenzMOI-BM [registered trademark], manufactured by Showa Denko K.K.), and 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate (KarenzMOI-BP [registered trademark], manufactured by Showa Denko K.K.). These compounds may be used alone or in combination to produce polymers, or may be combined with other compounds to produce polymers.

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

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

When the (E) component is selected as the crosslinking agent in the first photosensitive resin composition of the present invention, the content is 1 to 50 parts by mass, preferably 1 to 40 parts by mass, and more preferably 1 to 30 parts by mass, per 100 parts by mass of the (A) component. If the content of the crosslinkable compound is low, the density of the crosslinks formed by the crosslinkable compound is insufficient, and the effect of improving the heat resistance, solvent resistance, resistance to long-term baking, etc. after pattern formation may not be obtained. On the other hand, if it exceeds 50 parts by mass, uncrosslinked crosslinkable compound is present, and the heat resistance, solvent resistance, resistance to long-term baking, etc. after pattern formation may decrease, and the storage stability of the photosensitive resin composition may be deteriorated.

<Component (F)>
The component (F) is a compound having two or more ethylenically polymerizable groups. The compound having two or more ethylenically polymerizable groups means a compound having two or more polymerizable groups in one molecule, and the polymerizable groups are located at the molecular terminals, and the polymerizable groups mean at least one type of 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 as component (F) is preferably a compound having a molecular weight of 1,000 or less (when the compound is a polymer, the weight average molecular weight) from the viewpoints of having good compatibility with each component in the solution of the negative type photosensitive resin composition in the first photosensitive resin composition of the present invention and not affecting the developability.

Specific examples of such compounds include dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol diacrylate, pentaerythritol dimethacrylate, tetramethylolpropane tetraacrylate, and tetramethylolpropane tetramethacrylate. , tetramethylolmethane tetraacrylate, tetramethylolmethane tetramethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, 1,3,5-triacryloylhexahydro-S-triazine, 1,3,5-trimethacryloylhexahydro-S-triazine, tris(hydroxyethylacryloyl)isocyanurate, tris(hydroxyethylmethacryloyl)isocyanurate, triacryloyl formal, trimethacryloyl formal, 1,6-hexanediol acrylate, 1,6-hexanediol meth acrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, ethanediol diacrylate, ethanediol dimethacrylate, 2-hydroxypropanediol diacrylate, 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 fluorene diacrylate, bisphenoxyethanol fluorene dimethacrylate, diallyl ether bisphenol A, o-diallyl bisphenol A, diallyl maleate, and triallyl trimellitate.

The above-mentioned polyfunctional acrylate compounds are readily available as commercial products. Specific examples thereof include, for example, KYARAD T-1420, KYARAD DPHA, KYARAD DPHA-2C, KYARAD D-310, KYARAD D-330, KYARAD DPCA-20, KYARAD DPCA-30, KYARAD DPCA-60, KYARAD DPCA-120, KYARAD DN-0075, KYARAD DN-2475, KYARAD R-526, KYARAD NPGDA, KYARAD PEG400DA, KYARAD MANDA, KYARAD R-167, KYARAD HX-220, KYARAD HX620, KYARAD R-551, KYARAD R-712, KYARAD R-604 ...712, KYARAD R-712, KYARAD R-712, KYARAD R-712, KYARAD R-712, KYARAD R-712, KYARAD R-712, KYARAD R-712, KYARAD R-712, KYARAD R-712 684, 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-131 0, M-1600, M-1960, M-8100, M-8530, M-8560, M-9050 (manufactured by Toagosei Co., Ltd.), Viscoat 295, 300, 360, G PT, 3PA, 400, 260, 312, 335HP (manufactured by Osaka Organic Chemical Industry Co., Ltd.), A-9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A-T MM-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 ethylenically polymerizable groups can be used alone or in combination of two or more.

When the first photosensitive resin composition of the present invention contains the component (F), the content is preferably 5 to 200 parts by mass, more preferably 10 to 150 parts by mass, and particularly preferably 50 to 150 parts by mass, relative to 100 parts by mass of the component (A). If this ratio is too small, the exposed part may not be cured sufficiently, and the pattern may not be formed, or even if it is formed, the film may be unreliable. If this ratio is too large, tack may occur in the coating film after prebaking, or the unexposed part may not dissolve well during development.

<(G) component>
The component (G) 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, such as an epoxy group, an alkoxymethyl group, a hydroxymethyl group, etc.

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, glycerol triglycidyl ether, diethylene glycol diglycidyl ether, 2,6-diglycidylphenyl glycidyl ether, 1,1,3-tris[p-(2,3-epoxypropoxy)phenyl]propane, 1,2-cyclohexanedicarboxylic acid diglycidyl ester, 4,4'-methylenebis(N,N-diglycidylaniline), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, trimethylolethane triglycidyl ether, bisphenol-A-diglycidyl ether, and pentaerythritol polyglycidyl ether.

As the compound having two or more epoxy groups, a commercially available compound may be used since it is easily available. Specific examples (product names) of the epoxy resins include, but are not limited to, epoxy resins having an amino group, such as YH-434 and YH434L (manufactured by Shin-Nikka Epoxy Manufacturing Co., Ltd.); epoxy resins having a cyclohexene oxide structure, such as Epolead GT-401, GT-403, GT-301, GT-302, Celloxide 2021, and Celloxide 3000 (manufactured by Daicel Corporation); bisphenol A type epoxy resins, such as Epicoat 1001, 1002, 1003, 1004, 1007, 1009, 1010, and 828 (all manufactured by Yuka Shell Epoxy Co., Ltd. (currently Mitsubishi Chemical Corporation)); and bisphenol A type epoxy resins, such as Epicoat 807 (manufactured by Yuka Shell Epoxy Co., Ltd. (currently Mitsubishi Chemical Corporation)). Epikote F type epoxy resins; phenol novolac type epoxy resins such as Epicoat 152 and 154 (both manufactured by Yuka Shell Epoxy Co., Ltd. (currently Mitsubishi Chemical Corporation)), EPPN 201 and 202 (both manufactured by Nippon Kayaku Co., Ltd.); EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, EOCN-102 Cresol novolac epoxy resins such as Epikote 180S75 (manufactured by Yuka Shell Epoxy Co., Ltd. (currently Mitsubishi Chemical Corporation)); Denacol EX-252 (manufactured by Nagase ChemteX Corporation), CY175, CY177, CY179, Araldite CY-182, CY-192, and CY-184 (manufactured by Huntsman Chemical Co., Ltd.);
alicyclic epoxy resins such as Epiclon 200 and 400 (manufactured by Dainippon Ink and Chemicals Co., Ltd. (currently DIC Corporation)), Epicoat 871 and 872 (manufactured by Yuka Shell Epoxy Co., Ltd. (currently Mitsubishi Chemical Corporation)), ED-5661 and ED-5662 (manufactured by Celanese Coatings Co., Ltd.); aliphatic polyglycidyl ethers such as Denacol EX-611, EX-612, EX-614, EX-622, EX-411, EX-512, EX-522, EX-421, EX-313, EX-314 and EX-321 (manufactured by Nagase ChemteX Corporation).

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

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

The weight average molecular weight of such a polymer 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.

Examples of compounds having two or more substituents selected from alkoxymethyl groups and hydroxymethyl groups include compounds such as alkoxymethylated glycoluril, alkoxymethylated benzoguanamine, and alkoxymethylated melamine, as well as phenoplast-based compounds.

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

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

Specific examples of alkoxymethylated melamines 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 the hydrogen atom of the amino group is substituted with a methylol group or an alkoxymethyl group. For example, there may be mentioned high molecular weight compounds produced from melamine compounds and benzoguanamine compounds described in U.S. Pat. No. 6,323,310. Commercially available products of the melamine compounds include Cymel (registered trademark) 303 (manufactured by Mitsui Cytec Co., Ltd.), and commercially available products of the benzoguanamine compounds include Cymel (registered trademark) 1123 (manufactured by Mitsui Cytec Co., Ltd.).

Specific examples of phenoplast compounds are as described in paragraph [0112] above.

Furthermore, as component (G), polymers produced using acrylamide compounds or methacrylamide compounds substituted with hydroxymethyl groups or alkoxymethyl groups, such as N-hydroxymethylacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethylacrylamide, and N-butoxymethylmethacrylamide, can also be used.

Examples of such polymers include poly(N-butoxymethylacrylamide), a copolymer of N-butoxymethylacrylamide and styrene, a copolymer of N-hydroxymethylmethacrylamide and methyl methacrylate, a copolymer of N-ethoxymethylmethacrylamide and benzyl methacrylate, and a copolymer of N-butoxymethylacrylamide, benzyl methacrylate, and 2-hydroxypropyl methacrylate, etc. The weight average molecular weight of such polymers is 1,000 to 50,000, preferably 1,500 to 20,000, and 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 the acid of component (G), the content is preferably 5 to 200 parts by mass, more preferably 50 to 150 parts by mass, based on 100 parts by mass of component (A). If this ratio is too small, the photocurability of the negative photosensitive resin composition may decrease, while if it is too large, the developability of the unexposed parts may decrease, causing a residual film or residue.

<Other additives>
Furthermore, the first photosensitive resin composition used in the present invention may contain, as necessary, a leveling agent, a rheology adjuster, a pigment, a dye, a storage stabilizer, an antifoaming agent, an adhesion promoter, or a dissolution promoter such as a polyhydric phenol or a polyvalent carboxylic acid, as long as the effects of the present invention are not impaired.

<Resist film forming process>
After the underlayer film 12 is formed as described above, a second photosensitive resin composition containing a liquid-repellent component is applied onto the underlayer film 12 and prebaked to form a resist film 13 for the liquid-repellent bank (FIG. 1). Usually, this second photosensitive resin composition is applied onto the entire surface of the underlayer film 12 to form the resist film 13 for the liquid-repellent bank.
Each component of the resist film for the liquid repellent bank will be described in detail below.

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

An active methylene group refers to a methylene group ( _-CH2- ) that has a carbonyl group adjacent to it and is reactive to nucleophiles. In the present invention, the active methine group refers to an active methylene group in which one hydrogen atom of the methylene group is substituted with an alkyl group and is reactive to nucleophiles.

Among the active methylene groups and active methine groups, the active methylene groups are preferred, and the 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), examples of the alkyl group represented by R include alkyl groups having 1 to 20 carbon atoms, and alkyl groups having 1 to 5 carbon atoms are preferred.
Examples of such an alkyl group include a methyl group, an ethyl group, an n-propyl group, and an i-propyl group.
Of these, a methyl group, an ethyl group, an n-propyl group, etc. are preferred.

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

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

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

The alkali-soluble resin of component (a) above may be an alkali-soluble resin having such a structure, and there are no particular limitations on the main chain skeleton and the type of side chain of the polymer constituting the resin.

However, the number average molecular weight of the alkali-soluble resin of component (a) is within the range of 2,000 to 50,000. If the number average molecular weight is too high, exceeding 50,000, development residues are likely to be generated and sensitivity will decrease significantly, while if the number average molecular weight is too low, below 2,000, a considerable amount of film loss will occur in the exposed areas during development, which may result in insufficient curing.

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

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

That is, the specific copolymer is a copolymer formed from, as essential constituent units, a monomer exhibiting alkali solubility, i.e., a monomer having at least one monomer selected from the group consisting of a phenolic hydroxyl group and a carboxyl group, and at least one monomer selected from the group of monomers copolymerizable with these monomers, and has a number average molecular weight of 2,000 to 50,000. If the number average molecular weight is more than 50,000, residues may be generated.

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

Specific examples of the monomer are given below, but the monomer is 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, and N-(carboxyphenyl)acrylamide.

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

The ratio of the unsaturated carboxylic acid derivative and/or the monomer having a phenolic hydroxyl group and a polymerizable unsaturated group in the production of the alkali-soluble resin of component (a) is preferably 5 mol% to 90 mol%, more preferably 10 mol% to 60 mol%, and most preferably 10 mol% to 30 mol% of all the monomers used in the production of the alkali-soluble resin of component (a). If the unsaturated carboxylic acid derivative is less than 5% by weight, the polymer will have insufficient alkali solubility.

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

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, and 5-acryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone.

The ratio of the monomer having a hydroxyalkyl group and a polymerizable unsaturated group in the production of the alkali-soluble resin of component (a) is preferably 5% to 60% by mass, more preferably 10% to 50% by mass, and most preferably 20% to 40% by mass. If 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 it is 60% by mass or more, the alkali-soluble group of component (a) may be insufficient, and characteristics such as developability may be deteriorated.

The alkali-soluble resin which is the component (a) of the present invention is preferably one which has been further copolymerized with an N-substituted maleimide compound in order to increase 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, compounds that do not have an aromatic ring are preferred, and from the viewpoints of developability, transparency, and heat resistance, compounds that have an alicyclic skeleton are more preferred, and among these, cyclohexylmaleimide is the most preferred.

The ratio of N-substituted maleimide in the production of the alkali-soluble resin of component (a) 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 is less than 5% by mass, the Tg of the copolymer may be low and the heat resistance may be poor. If it is 60% by mass or more, the transparency may be reduced.

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 is preferably a copolymer further having a self-crosslinking group or further having a group (hereinafter also referred to as a crosslinking group) that reacts with at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, and an amino group.

The above-mentioned self-crosslinking groups include N-alkoxymethyl groups, N-hydroxymethyl groups, alkoxysilyl groups, epoxy groups, oxetane groups, vinyl groups, and blocked isocyanate groups.

Examples of the crosslinkable group include an N-alkoxymethyl group, an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, a vinyl group, and a blocked isocyanate group.

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

When the alkali-soluble resin of component (a) further has a repeating unit having at least one self-crosslinking group selected from N-alkoxymethyl groups, N-hydroxymethyl groups, alkoxysilyl groups, epoxy groups, oxetane groups, vinyl groups, and blocked isocyanate groups, and crosslinking groups such as N-alkoxymethyl groups, N-hydroxymethyl groups, alkoxysilyl groups, epoxy groups, vinyl groups, and blocked isocyanate groups, for example, it is sufficient to copolymerize an unsaturated compound that has radical polymerizability and has at least one crosslinking group selected from epoxy groups, oxetane groups, vinyl groups, and blocked isocyanate groups, and self-crosslinking groups such as N-alkoxymethyl groups, N-hydroxymethyl groups, and alkoxysilyl groups.

Examples of unsaturated compounds that are radically polymerizable and have an N-alkoxymethyl group include N-butoxymethylacrylamide, N-isobutoxymethylacrylamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, and N-methylolacrylamide.

Examples of monomers that are radically polymerizable and further have an N-hydroxymethyl group include N-hydroxymethylacrylamide and N-hydroxymethylmethacrylamide.

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

Examples of unsaturated compounds having radical polymerization properties and further having an epoxy group include glycidyl acrylate, glycidyl methacrylate, α-ethyl glycidyl acrylate, α-n-propyl glycidyl acrylate, α-n-butyl glycidyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl methacrylate, α-ethyl acrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and 3,4-epoxycyclohexyl methacrylate. Of these, glycidyl methacrylate, 6,7-epoxyheptyl methacrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and 3,4-epoxycyclohexyl methacrylate are preferably used. These can be used alone or in combination.

Examples of unsaturated compounds having radical polymerization properties and further 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 are preferred, and 3-(methacryloyloxymethyl)-3-ethyl-oxetane, 3-(acryloyloxymethyl)-3-ethyl-oxetane, etc. are preferably used.

Examples of monomers that are radically polymerizable and further have a vinyl group include 2-(2-vinyloxyethoxy)ethyl acrylate and 2-(2-vinyloxyethoxy)ethyl methacrylate.

Examples of monomers that are radically polymerizable and further have a blocked isocyanate group include 2-(0-(1'-methylpropylideneamino)carboxyamino)ethyl methacrylate and 2-(3,5-dimethylpyrazolyl)carbonylamino)ethyl methacrylate.

When the second photosensitive resin composition of the present invention satisfies (z1), it contains a structural unit derived from an unsaturated compound having radical polymerizability and at least one group selected from self-crosslinking groups such as N-alkoxymethyl groups, N-hydroxymethyl groups, alkoxysilyl groups, epoxy groups, oxetane groups, vinyl groups, and blocked isocyanate groups, and crosslinking groups such as N-alkoxymethyl groups, N-hydroxymethyl groups, alkoxysilyl groups, epoxy groups, vinyl groups, and blocked isocyanate groups, in an amount of preferably 10% to 70% by mass, particularly preferably 20% to 60% by mass, based on the total of all repeating units contained in the alkali-soluble resin of component (a). If the amount of this structural unit is less than 10% by mass, the heat resistance and surface hardness of the obtained cured film tend to decrease, while if the amount of this structural unit exceeds 70% by mass, the storage stability of the radiation-sensitive resin composition tends to decrease.

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

Examples of the acrylic acid ester compounds 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, and methoxytriethylene glycol acrylate. acrylate, 2-ethoxyethyl acrylate, 2-aminoethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl 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 methacrylic acid ester 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- Examples include ethoxyethyl methacrylate, 2-aminomethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl 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, and poly(ethylene glycol) ethyl ether methacrylate.

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

Examples of the vinyl compounds include methyl vinyl ether, benzyl vinyl ether, cyclohexyl vinyl ether, vinyl naphthalene, vinyl anthracene, vinyl carbazole, allyl glycidyl ether, 3-ethenyl-7-oxabicyclo[4.1.0]heptane, 1,2-epoxy-5-hexene, and 1,7-octadiene monoepoxide.

The styrene compound includes styrenes that do not have a hydroxy group, such as styrene, α-methylstyrene, chlorostyrene, and bromostyrene.

In the production of the alkali-soluble resin, which is component (a), the ratio of the above 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 it exceeds 80% by mass, the amount of essential components will be relatively reduced, making it difficult to fully 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, but for example, it can be obtained by carrying out a polymerization reaction at a temperature of 50°C to 110°C in a solvent in which a monomer having at least one selected from the group consisting of a carboxyl group, a phenolic hydroxyl group, and a group that generates a carboxylic acid or a phenolic hydroxyl group by the action of heat or acid, a monomer having a hydroxyalkyl group, and optionally a monomer having at least one group selected from a self-crosslinking group such as an N-alkoxymethyl group, an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, an oxetane group, a vinyl group, and a blocked isocyanate group, and a crosslinking group such as an N-alkoxymethyl group, an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, a vinyl group, and a blocked isocyanate group, and optionally other copolymerizable monomers and optionally a polymerization initiator, etc. are present. In this case, the solvent used is not particularly limited as long as it dissolves the monomer constituting the alkali-soluble resin and the acrylic polymer having a specific functional group. Specific examples include the solvents described in the component (c) described later.

The acrylic polymer having specific functional groups 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 can be reprecipitated by adding diethyl ether or water under stirring, and the resulting precipitate can be filtered and washed, and then dried at room temperature or by heating under normal pressure or reduced pressure to obtain a powder of the specific copolymer. By such an operation, the polymerization initiator and unreacted monomers coexisting with the specific copolymer can be removed, and as a result, a powder of the purified specific copolymer can be obtained. If the specific copolymer cannot be sufficiently purified by one operation, the obtained powder can be redissolved in a solvent and the above operation can be repeated.
In the present invention, the powder of the specific copolymer may be used as it is, or the powder may be redissolved in, for example, the component (c) described below and used in the form of a solution.

In addition, 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 also be used, and there is no particular limitation on the type of these that can be used as long as they are alkali-soluble.

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

The (i) tetracarboxylic acid dianhydride compound is not particularly limited, and specific examples thereof include aromatic tetracarboxylic acids such as pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 3,3',4,4'-benzophenonetetracarboxylic acid dianhydride, 3,3',4,4'-diphenylethertetracarboxylic acid dianhydride, and 3,3',4,4'-diphenylsulfonetetracarboxylic acid dianhydride; 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride; and 1,2-dimethyl-1,2,3,4-cyclopentanetetracarboxylic acid dianhydride. Examples of the tetracarboxylic acid dianhydride include alicyclic tetracarboxylic acid dianhydrides such as cyclobutane tetracarboxylic acid dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,2,3,4-cyclopentane tetracarboxylic acid dianhydride, 1,2,3,4-cyclohexane tetracarboxylic acid dianhydride, and 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid dianhydride, and aliphatic tetracarboxylic acid dianhydrides such as 1,2,3,4-butane tetracarboxylic acid dianhydride.
These may be used alone or in combination of two or more compounds.

The diamine compound (j) is not particularly limited, and examples thereof include 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, 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- 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)methane biphenyl) 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]sulfone, diamine compounds having a phenolic hydroxy group such as 2,2-bis[4-(3-amino-4-hydroxyphenoxy)phenyl]propane and 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)hexafluoropropane, Examples of the diamine compounds include diamine compounds having a thiophenol group such as isopropyl alcohol, and diamine compounds having a sulfonic acid group such as 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, and 4,4'-diamino-3,3'-dimethylbiphenyl-6,6'-disulfonic acid. In addition, p-phenylenediamine, m-phenylenediamine, and 4,4'-methylene-bis(2,6-ethylaniline) are also included.
, 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, Examples of diamine compounds include 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-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, and 2,2'-bis(trifluoromethyl)benzidine.
These may be used alone or in combination of two or more compounds.

When the polyamic acid used in the present invention is produced from (i) a tetracarboxylic dianhydride compound and (j) a diamine compound, the compounding ratio of the two compounds, i.e., the total number of moles of (j) diamine compound/the total number of moles of (i) tetracarboxylic dianhydride compound, is preferably 0.7 to 1.2. As with a normal polycondensation reaction, the closer this molar ratio is to 1, the greater the degree of polymerization of the polyamic acid produced, and the greater the molecular weight.

In addition, when polymerization is carried out using an excess of a diamine compound, the terminal amino groups of the remaining polyamic acid can be protected by reacting them with a carboxylic acid anhydride.
Examples of such carboxylic acid anhydrides include phthalic anhydride, trimellitic anhydride, maleic anhydride, naphthalic anhydride, hydrogenated phthalic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, itaconic anhydride, and tetrahydrophthalic anhydride.

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 any temperature range of −20° C. to 150° C., preferably −5° C. to 100° C. To obtain a high molecular weight polyamic acid, the reaction temperature is appropriately selected from the range of 5° C. to 40° C. and the reaction time is appropriately selected from the range of 1 hour to 48 hours. To obtain a low molecular weight, partially imidized polyamic acid with high storage stability, it is more preferable to select the reaction temperature from 40° C. to 90° C. and the reaction time from 10 hours or more.
When the terminal amino group is protected with an acid anhydride, the reaction temperature can be selected from the range of -20°C to 150°C, preferably -5°C to 100°C.

The reaction of the diamine compound with the tetracarboxylic dianhydride compound can be carried out in a solvent. Examples of the solvent 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, ethyl 3-ethoxypropionate, ethyl 2-ethoxypropionate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ... Examples of the solvent include ethylene 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, and 2-heptanone. These may be used alone or in combination. Furthermore, even if the solvent does not dissolve polyamic acid, it may be mixed with the above solvent and used within the range in which the polyamic acid produced by the polymerization reaction does not precipitate.

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

In addition, any polyimide can be used as component (a). The polyimide used in the present invention is a polyimide precursor such as the polyamic acid that has been chemically or thermally imidized to 50% or more.

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

Such a polyimide can be obtained by synthesizing a polyimide precursor such as the above-mentioned polyamic acid, and then carrying out chemical imidization or thermal imidization.
A typical method for chemical imidization is to add excess acetic anhydride and pyridine to a polyimide precursor solution and react them at room temperature to 100° C. A typical method for thermal imidization is to heat a polyimide precursor solution at a temperature of 180° C. to 250° C. while dehydrating it.

In addition, phenol novolac resin can also be used as the alkali-soluble resin of component (a).

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

In addition, in the present invention, the alkali-soluble resin of component (a) may be a mixture of multiple types of alkali-soluble resins.

<(b) component>
The component (b) is a polymer having a liquid repellent group (b1).

In the present invention, examples of the polymer include polyimide, polyamic acid, polyamide, polyurea, polyurethane, phenolic resin, epoxy resin, polysiloxane, polyester, and acrylic polymer, and a preferred polymer is acrylic polymer.

Here, acrylic polymer refers to a polymer obtained using a monomer having a polymerizable unsaturated group, such as an acrylic acid ester, a methacrylic acid ester, styrene, or maleimide, i.e., a polymerizable group containing a C=C double bond in the structure.

Examples of polyamic acids, polyimides, polyamides, and polyureas include polyamic acids obtained by reacting diamines with acid dianhydrides, polyimides obtained by imidizing the polyamic acids, polyamides obtained by reacting diamines with dicarboxylic anhydrides, and polyureas obtained by reacting diamines with diisocyanates, and further include polymers obtained from a monomer mixture containing at least one monomer having a fluoroalkyl group or fluoroalkoxy group and at least one monomer having a hydroxyl group.

Examples of 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.

An example of a phenolic resin is novolac resin, which is obtained by polymerizing phenol having a fluoroalkyl group or a fluoroalkoxy group with formaldehyde.

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

Examples of polysiloxanes include polymers obtained by polymerizing 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.

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.

<(b1) Introduction of Liquid Repellent Group>
The liquid repellent group may be, for example, at least one group selected from a fluoroalkyl group having 3 to 10 carbon atoms, a polyfluoroether group, a silyl ether group, and a polysiloxane group.

The fluoroalkyl group has 3 to 10 carbon atoms, and preferably has 4 to 10 carbon atoms.
Examples of such fluoroalkyl groups include 2,2,2-trifluoroethyl groups, 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-methylhexyl)ethyl group, 2-(perfluoro-5-methylhexyl)-2-hydroxypropyl group, 2-(perfluoro-7-methyloctyl)ethyl group, and 2-(perfluoro-7-methyloctyl)-2-hydroxypropyl group.

To introduce a fluoroalkyl group having 3 to 10 carbon atoms into the polymer, which is component (b) 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 component (b) is an acrylic polymer include 2,2,2-trifluoroethyl acrylate, 2,2,2-trifluoroethyl 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-hydroxy Propyl 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-5-methylhexyl)ethyl acrylate, 2-(perfluoro-5-methylhexyl)ethyl 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, and 2-(perfluoro-7-methyloctyl)-2-hydroxypropyl methacrylate.

The polyfluoroether group includes an Rf group having a polyfluoroether structure represented by the following formula 2.
-(X-O) _n -Y...Formula 2
In formula 2, X represents 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 grouped by n represents the same or different groups, Y represents a hydrogen atom (only when a fluorine atom is not bonded to the carbon atom adjacent to the oxygen atom adjacent to Y), a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or a fluorinated monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and n represents an integer from 2 to 50, with the proviso that the total number of fluorine atoms in formula 2 is 2 or more.

As a preferred embodiment of X and Y in formula 2, X is an alkylene group having 1 to 10 carbon atoms that has been fluorinated by removing one hydrogen atom, or a perfluorinated alkylene group having 1 to 10 carbon atoms, and each unit grouped by n represents the same group or a different group, and Y represents an alkyl group having 1 to 20 carbon atoms that has been fluorinated by removing one hydrogen atom, or a perfluorinated alkyl group having 1 to 20 carbon atoms.

As a more preferred embodiment of X and Y in formula 2, X is a perfluorinated alkylene group having 1 to 10 carbon atoms, and each unit bounded by n may be the same or different, and Y is a perfluorinated alkyl group having 1 to 20 carbon atoms.

In formula 2, n represents an integer of 2 to 50. n is preferably 2 to 30, and more preferably 2 to 15. When n is 2 or more, the liquid repellency is good. When n is 50 or less, when the polymer, which is component (b), is synthesized by copolymerizing a monomer having an Rf group with 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, or with another monomer, the compatibility of the monomers is good.

The total number of carbon atoms in the Rf group consisting of the polyfluoroether structure represented by formula 2 is preferably 2 to 50, more preferably 2 to 30. Within this range, the polymer of component (b) exhibits good liquid repellency. In addition, when the polymer of component (b) is synthesized by copolymerizing a monomer having an Rf group with 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, or with other monomers, the compatibility of the monomers is good.

Specific examples of X include -CF2- _{, -CF2CF2-} , _-CF2CF2CF2- , _{-CF2CF ( CF3} )-, _{-CF2CF2CF2CF2CF2- , -CF2CF2CF ( CF3} ) _{- ,} and _CF2CF ( _{CF3 ) CF2- .}

Specific examples of Y include -CF3, _-CF2CF3 , _-CF2CHF2 , _{-(CF2)2CF3, -(CF2)3CF3, -(CF2)4CF3 , - ( CF2 ) 5CF3 , - ( CF2 ) 6CF3 , - ( CF2 ) 7CF3 ,} -( _CF2 ) _8CF3 , -( _CF2 ) _{9CF3 ,} and ( _{CF2 ) 11CF3 , -} ( _CF2 ) _{15CF3 .}

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

Specific examples of the Rf group represented by formula 3 include:
—CF ₂ O(CF ₂ CF ₂ O) _n-1 CF ₃ (n is 2 to 9),
-CF( _CF3 )O( _CF2CF ( _CF3 )O) _{n- 1C6F13} (n is 2 to ₆ ),
-CF( _CF3 )O( _CF2CF ( _CF3 )O) _{n- 1C3F7} (n is 2 to ₆ )
are preferred from the viewpoint of ease of synthesis.

The Rf groups in the polymer that is component (b) may all be the same or different.

The silyl ether group means a group in which a hydroxy group of an alcohol is protected with a trialkylsilyl group, and is preferably a group represented by the following formula:
-X ⁴ -Si(O-SiX ¹ X ² X ³ ) ₃
(In the formula, ^X1 , ^X2 , and ^X3 each independently represent an alkyl group having 1 to 3 carbon atoms, and ^X4 represents an alkylene group having 1 to 6 carbon atoms.)

To introduce a silyl ether group into the polymer (b) of the present invention, a monomer having a silyl ether group may be copolymerized.

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

The polysiloxane group includes a group having a polysiloxane structure represented by formula 4. Hereinafter, the group having a polysiloxane structure represented by formula 4 will be referred to as a pSi group.
-(SiR ¹ R ² -O) _n -SiR ¹ R ² R ³ ...Formula 4
(wherein R ¹ and R ² independently represent a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group; R ³ represents a hydrogen atom or an organic group having 1 to 10 carbon atoms; and n represents an integer of 1 to 200).

^R1 and ^R2 independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, and may be the same or different for each siloxy unit. Since the polymer (b) exhibits good liquid repellency, it is preferable that ^R1 and ^R2 are a hydrogen atom, a methyl group, or a phenyl group, and more preferably, ^R1 and ^R2 of all siloxy units are a methyl group. ^R3 may also contain a nitrogen atom, an oxygen atom, or the like.

Methods for introducing pSi groups into the polymer (b), component, include copolymerizing a monomer having a pSi group, various modification methods in which a polymer having a reactive site is reacted with a compound having a pSi group, and a method using a polymerization initiator having a pSi group.

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

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

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

A method in which a monomer having an amino group is copolymerized in advance, and then a compound having an epoxy group at one end and a pSi group at the other end is reacted. A method in which a monomer having a carboxyl group is copolymerized in advance, and then a compound having an epoxy group at one end and a pSi group at the other end is reacted. A method in which a monomer having a carboxyl group is copolymerized in advance, and then a compound having an amino group at one end and a pSi group at the other end is reacted. A method in which a monomer having a carboxyl group is copolymerized in advance, and then a compound having a silyl chloride group at one end and a pSi group at the other end is reacted.
A method of reacting a compound having an i group with a monomer having a hydroxy group, and then reacting the monomer with a compound having a silyl chloride group at one end and a pSi group at the other 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 group having a monovalent polysiloxane structure at the terminal portion or side chain of the initiator molecule. Examples of initiators that contain a group having a divalent polysiloxane structure in the main chain of the initiator molecule include compounds that alternate between a group having a divalent polysiloxane structure and an azo group. Commercially available products include VPS-1001 and VPS-0501 (both manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.).

It is preferable that component (b) is further a polymer having (b2): a group selected from an N-alkoxymethylamide group, a blocked isocyanate group, and a trialkoxysilyl group.

<(b2): Introduction of a group selected from an N-alkoxymethylamide group, a blocked isocyanate group, and a 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 which is component (b), a monomer having a group selected from an N-alkoxymethylamide group, a blocked isocyanate group, and a trialkoxysilyl group may be copolymerized.

When component (b) is an acrylic polymer, examples of monomers having an N-alkoxymethylamide group include (meth)acrylamide compounds substituted with a hydroxymethyl group or an alkoxymethyl group, such as N-hydroxymethyl(meth)acrylamide, N-methoxymethyl(meth)acrylamide, N-ethoxymethyl(meth)acrylamide, and N-butoxymethyl(meth)acrylamide.

When component (b) is an acrylic polymer, examples of monomers having a blocked isocyanate group include 2-(0-(1'-methylpropylideneamino)carboxyamino)ethyl methacrylate, 2-(3,5-dimethylpyrazolyl)carbonylamino)ethyl methacrylate, etc.

When component (b) is an acrylic polymer, examples of monomers having a trialkoxysilyl group include 3-trimethoxysilylpropyl acrylate, 3-triethoxysilylpropyl acrylate, 3-trimethoxysilylpropyl methacrylate, and 3-triethoxysilylpropyl methacrylate.

It is preferable that the component (b) is a polymer further having (b3) at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group, and an amino group.

<(b3) Introduction of at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group, and an amino group>
In order to introduce (b3) at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group, and an amino group into the polymer, which is the component (b) of the present invention, a monomer having (b3) at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group, and an amino group may be copolymerized.

When component (b) is an acrylic polymer, examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, mono-(2-(acryloyloxy)ethyl)phthalate, mono-(2-(methacryloyloxy)ethyl)phthalate, N-(carboxyphenyl)maleimide, N-(carboxyphenyl)methacrylamide, and N-(carboxyphenyl)acrylamide.

When component (b) 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 acrylate, 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 Examples of the monomers include 5-acryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone, 5-methacryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone, p-hydroxystyrene, α-methyl-p-hydroxystyrene, N-hydroxyphenylmaleimide, N-hydroxyphenylacrylamide, N-hydroxyphenylmethacrylamide, p-hydroxyphenylacrylate, and p-hydroxyphenylmethacrylate. Among these, monomers selected from 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate are preferred.

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

When component (b) is an acrylic polymer, examples of monomers having an amino group include aminoethyl acrylate, aminoethyl methacrylate, aminopropyl acrylate, and aminopropyl methacrylate.

When component (b) is an acrylic polymer, the polymer of component (b) can be produced by polymerizing 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, and optionally a monomer having at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group, and an amino group, at a temperature of 50°C to 110°C in a solvent in the presence of a polymerization initiator. The solvent used is not particularly limited as long as it dissolves the monomer that constitutes the alkali-soluble polymer and the polymer having a specific functional group. Specific examples include the solvents described in component (c) below.

Specific examples of other monomers b include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, glycidyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, 2-aminomethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, γ-butyrolactone methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, 8-ethyl-8-tricyclodecyl methacrylate, methyl acrylate, ethyl acrylate, isopropyl a 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-tricyclodecyl acrylate, 8-ethyl-8-tricyclodecyl acrylate, N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, styrene, vinyl naphthalene, vinyl anthracene, and vinyl biphenyl.

The polymer having specific functional groups 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 can be reprecipitated by adding diethyl ether or water under stirring, and the resulting precipitate can be filtered and washed, and then dried at room temperature or by heating under normal pressure or reduced pressure to obtain a powder of the specific copolymer. By such an operation, the polymerization initiator and unreacted monomers coexisting with the specific copolymer can be removed, and as a result, a powder of the purified specific copolymer can be obtained. If the specific copolymer cannot be sufficiently purified by one operation, the obtained powder can be redissolved in a solvent and the above operation can be repeated.
In the present invention, the powder of the specific copolymer may be used as it is, or the powder may be redissolved in, for example, the component (c) described below and used in the form of a solution.

In the polymer of component (b) above, the amount of liquid repellent group (b1) introduced is preferably 5 mol% to 60 mol% of the total repeating units, and more preferably 5 mol% to 40 mol%. If it is less than 5 mol%, the liquid repellency effect may not be achieved. If it is more than 60 mol%, problems such as aggregation may occur.

In the polymer of component (b) above, the amount of group (b2) selected from an N-alkoxymethylamide group, a blocked isocyanate group, and a trialkoxysilyl group introduced is preferably 5 mol % to 70 mol %, and more preferably 5 mol % to 50 mol %, based on the total repeating units. If it is less than 5 mol %, problems may arise with the heat resistance and solvent resistance of the resulting film. If it is more than 60 mol %, it may affect developability.

When at least one group (b3) selected from the group consisting of hydroxyl, carboxyl, amide and amino groups is introduced into the polymer of component (b) above, the amount introduced is preferably 5 mol% to 60 mol%, more preferably 5 mol% to 40 mol%, based on the total repeating units. If it is less than 5 mol%, the effect of improving the heat resistance and solvent resistance of the resulting 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 (b) is preferably 2,000 to 100,000. More preferably, it is 3,000 to 50,000, and even more preferably, it is 4,000 to 10,000. If the number average molecular weight is greater than 100,000, residues may be generated.

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

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

When the component (a) has a liquid repellent group (b1) in the component (b), the component (a) can also serve as the component (b), and in this case it is not always necessary to use the component (b).
In this case, it is preferable that the polymerized unit (monomer) having the liquid repellent group (b1) accounts for 5 to 30 parts by mass per 100 parts by mass of the component (a).

<(c) component>
The component (c) used in the present invention serves as a solvent that dissolves the components (a), (b), and, if necessary, the components (d), (e), (f), and (g) described below, and also dissolves other additives that are added as desired, as described below. As long as the solvent has such dissolving ability, there are no particular limitations on the type or structure of the solvent.

Such component (c) can be the same as the component (C) used in the composition for forming the upper layer film described above.

These solvents may be used alone or in combination of two or more.
Of these components (c), solvents not having a hydroxy group are preferred in terms of not dissolving the underlayer film, namely, 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, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone, etc. These solvents are generally used as solvents for photoresist materials.
When using a solvent having a hydroxyl group, it is preferable to use it in combination with a solvent having no hydroxyl group, so as not to dissolve the underlayer film as described above. The solvent to be combined is not particularly limited, and may be one or more kinds, as long as it has good coating properties and does not dissolve the underlayer film. In this case, the amount of the solvent having a hydroxyl group is preferably 70% by weight or less, more preferably 60% by weight or less, even more preferably 50% by weight or less, and most preferably 30% by weight or less, based on the total amount of the (c) component, so as not to dissolve the underlayer film.

<(d) component>
Examples of the photosensitizer that is the component (d) include (d-1) a 1,2-quinonediazide compound, (d-2) a photoradical generator, and (d-3) a photoacid generator.

(d-1) Examples of the 1,2-quinone diazide compound include the same compounds as (D-1) listed in the component (D) used in the composition for forming the upper layer film described above.

When the second photosensitive resin composition of the present invention is a positive photosensitive resin composition, the content of the compound having a quinone diazide group as component (d-1) is preferably 5 to 100 parts by mass, more preferably 8 to 50 parts by mass, and even more preferably 10 to 40 parts by mass, relative to 100 parts by mass of the total of components (a) and (b). Alternatively, when component (a) has a liquid repellent group (b1) in component (b) and does not contain component (b), the content of component (d-1) is preferably 5 to 100 parts by mass, more preferably 8 to 50 parts by mass, and even more preferably 10 to 40 parts by mass, relative to 100 parts by mass of component (a).
0 parts by mass. If it is less than 5 parts by mass, the difference in dissolution rate between the exposed and unexposed parts of the positive photosensitive resin composition in the developer may become small, making patterning by development difficult. If it exceeds 100 parts by mass, the 1,2-quinone diazide compound may not be sufficiently decomposed by short-term exposure to light, resulting in a decrease in sensitivity, or the component (d-1) may absorb light, resulting in a decrease in transparency of the cured film.

(d-2) The photoradical generator is not particularly limited as long as it generates radicals upon exposure to light. Specific examples include the same substances as (D-2) listed in the component (D) used in the composition for forming the upper layer film described above.

When the second photosensitive resin composition of the present invention contains the component (d-2), the content is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, and particularly preferably 1 to 15 parts by mass, relative to 100 parts by mass of the total of the components (a) and (b). Alternatively, when the component (a) has the liquid repellent group (b1) in the component (b) and does not contain the component (b), the content of the component (d-2) is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, and particularly preferably 1 to 15 parts by mass, relative to 100 parts by mass of the component (a). If this ratio is too small, the exposed part may not be cured sufficiently, and the pattern may not be formed, or even if it is formed, the film may be unreliable. If this ratio is too large, the transmittance of the coating film may decrease, or the unexposed part may be poorly developed.

The photoacid generator (d-3) is not particularly limited as long as it is a compound that generates an acid by photodecomposition when irradiated with ultraviolet light. Examples of the acid generated when the photoacid generator is photodecomposed include the same acids generated when the photoacid generators listed in (D-3) of the component (D) used in the composition for forming the upper layer film described above are photodecomposed.

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

When the second photosensitive resin composition of the present embodiment contains the component (d-3), the content is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 8 parts by mass, based on 100 parts by mass of the total of the components (a) and (b). Alternatively, when the component (a) has the liquid repellent group (b1) in the component (b) and does not contain the component (b), the content of the component (d-3) is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 8 parts by mass, based on 100 parts by mass of the component (a). By setting the content of the component (d-3) to 0.01 parts by mass or more, sufficient thermosetting properties and solvent resistance can be imparted. However, if the content is more than 20 parts by mass, the unexposed portion may be poorly developed, or the storage stability of the composition may be reduced.

<(e) Component>
The component (e) is a crosslinking 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 thermally reactive site (e.g., carboxyl group and/or phenolic hydroxy group) of the component (a). Specific examples are given below, but are not limited thereto. The thermal crosslinking agent is preferably selected from, for example, (e1) a crosslinking compound having two or more substituents selected from an alkoxymethyl group and a hydroxymethyl group, or (e2) a crosslinking compound represented by the following formula (5). These crosslinking agents can be used alone or in combination of two or more.

When the crosslinkable compound (e1) having two or more substituents selected from alkoxymethyl groups and hydroxymethyl groups is exposed to high temperatures during thermal curing, the crosslinking reaction proceeds by a dehydration condensation reaction. Examples of such compounds include compounds such as alkoxymethylated glycoluril, alkoxymethylated benzoguanamine, and alkoxymethylated melamine, as well as phenoplast-based compounds.

Specific examples of alkoxymethylated glycoluril that can be used include those listed as component (E) used in the composition for forming the upper layer film described above.

Specific examples of the alkoxymethylated benzoguanamine that can be used are the same as those exemplified as the component (E) used in the composition for forming the upper layer film described above.

Specific examples of phenoplast-based compounds that can be used are the same as those listed in component (E) used in the composition for forming the upper layer film described above.

Furthermore, as component (e1), polymers produced using acrylamide compounds or methacrylamide compounds substituted with hydroxymethyl groups or alkoxymethyl groups, such as N-hydroxymethylacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethylacrylamide, and N-butoxymethylmethacrylamide, can also be used.

Such a polymer can be the same as (E1) listed in the component (E) used in the composition for forming the upper layer film described above.

The second photosensitive resin composition of the present invention can use, as component (e2), the same (E2) as that listed in the component (E) used in the composition for forming the upper layer film described above.

In addition, as component e, compounds other than those shown as components (e1) and (e2) that can form a crosslinked structure by thermal reaction with the thermally reactive sites of component (a) (e.g., carboxyl groups and/or phenolic hydroxyl groups) can also be used. Specific examples of the epoxy compounds include 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-hexanediol diglycidyl ether, glycerin 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; VESTANAT B1358/100, VESTAGON BF Examples of isocyanate compounds include Takenate (registered trademark) B-882N and Takenate (registered trademark) B-7075 (both are isocyanurate-modified polyisocyanates manufactured by Mitsui Chemicals, Inc.).

As the component (e), a polymer having two or more structures capable of forming a crosslinked structure by thermal reaction with the thermally reactive site (e.g., carboxyl group and/or phenolic hydroxy group) of the component (a) can be used. Specifically, for example, polymers produced using compounds having epoxy groups such as glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, etc., 3,4-epoxycyclohexylmethyl methacrylate, etc.,
Examples of the polymers include a polymer produced using a compound having an alkoxysilyl group such as -methacryloxypropyltrimethoxysilane, a compound having an isocyanate group such as 2-isocyanatoethyl methacrylate (KarenzMOI [registered trademark], manufactured by Showa Denko K.K.) and 2-isocyanatoethyl acrylate (KarenzAOI [registered trademark], manufactured by Showa Denko K.K.), and a compound having a blocked isocyanate group such as 2-(0-[1'-methylpropylideneamino]carboxyamino)ethyl methacrylate (KarenzMOI-BM [registered trademark], manufactured by Showa Denko K.K.) and 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate (KarenzMOI-BP [registered trademark], manufactured by Showa Denko K.K.). These compounds may be used alone or in combination to produce a polymer, or may be used in combination with other compounds to produce a polymer.

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

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

When the (e) component is selected as the crosslinking agent in the second photosensitive resin composition of the present invention, the content is 1 to 50 parts by mass, preferably 1 to 40 parts by mass, and more preferably 1 to 30 parts by mass, per 100 parts by mass of the total of the (a) and (b) components. Alternatively, when the (a) component has the (b1) liquid repellent group in the (b) component and does not contain the (b) component, the content of the (e) component is 1 to 50 parts by mass, preferably 1 to 40 parts by mass, and more preferably 1 to 30 parts by mass, per 100 parts by mass of the (a) component. When the content of the crosslinkable compound is low, the density of the crosslinks formed by the crosslinkable compound is insufficient, so that the effect of improving the heat resistance, solvent resistance, resistance to long-term baking, etc. after pattern formation may not be obtained. On the other hand, when it exceeds 50 parts by mass, uncrosslinked crosslinkable compound is present, and the heat resistance, solvent resistance, resistance to long-term baking, etc. after pattern formation may decrease, and the storage stability of the photosensitive resin composition may also deteriorate.

<Component (f)>
The component (f) is a compound having two or more ethylenically polymerizable groups. The compound having two or more ethylenically polymerizable groups means a compound having two or more polymerizable groups in one molecule, and the polymerizable groups are located at the molecular terminals, and the polymerizable groups mean at least one type of 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 as component (f) is preferably a compound having a molecular weight of 1,000 or less (when the compound is a polymer, the weight average molecular weight) from the viewpoints of having good compatibility with each component in the solution of the negative type photosensitive resin composition in the second photosensitive resin composition of the present invention and not affecting the developability.

Specific examples of such compounds include those listed in component (F) used in the composition for forming the upper layer film described above.

When the second photosensitive resin composition of the present invention contains the component (f), the content is preferably 5 to 200 parts by mass, more preferably 10 to 150 parts by mass, and particularly preferably 50 to 150 parts by mass, relative to 100 parts by mass of the total of the components (a) and (b). Alternatively, when the component (a) has the liquid repellent group (b1) in the component (b) and does not contain the component (b), the content of the component (f) is preferably 5 to 200 parts by mass, more preferably 10 to 150 parts by mass, and particularly preferably 50 to 150 parts by mass, relative to 100 parts by mass of the component (a). If this ratio is too small, the exposed part may not be cured sufficiently, and the pattern may not be formed, or even if it is formed, the film may be unreliable. If this ratio is too large, tack may occur in the coating film after pre-baking, or the unexposed part may not dissolve well 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 functional groups that form a covalent bond with an acid, the same ones as those listed in the component (G) used in the composition for forming the upper layer film described above 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 the acid of component (g), the content is preferably 5 to 200 parts by mass, more preferably 50 to 150 parts by mass, based on 100 parts by mass of the total of components (a) and (b). Alternatively, when component (a) has a liquid repellent group (b1) in component (b) and does not contain component (b), the content of component (g) is preferably 5 to 200 parts by mass, more preferably 50 to 150 parts by mass, based on 100 parts by mass of component (a). If this ratio is too small, the photocurability of the negative photosensitive resin composition may decrease, and on the other hand, if it is too large, the developability of the unexposed part may decrease, causing a residual film or residue.

<Other additives>
Furthermore, the second photosensitive resin composition used in the present invention may contain, as necessary, a leveling agent, a rheology adjuster, a pigment, a dye, organic/inorganic fine particles, a storage stabilizer, an antifoaming agent, an adhesion promoter, or a dissolution promoter such as a polyhydric phenol or a polyvalent carboxylic acid, as long as the effects of the present invention are not impaired.

<Bank Formation Process>
After the resist film 13 is formed, the underlayer film 12 and the resist film 13 are collectively patterned by exposure and development to form a bank. A region partitioned by the bank (non-bank portion) is formed in an opening 14 (FIG. 1).

As shown in FIG. 1, when the first and second photosensitive resin compositions are positive photosensitive resin compositions, the exposed portion is the non-bank portion, which is removed together with the underlayer film of the non-bank portion and the resist film of the non-bank portion during the development process 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 is the bank portion, which is removed together with the underlayer film of the non-bank portion and the resist film of the non-bank portion during the development process.

In the case of the conventional second photosensitive resin composition containing a liquid-repellent component, residues are left behind during the development process, making it difficult to remove them cleanly. The residues left behind cause defects such as unevenness in the organic thin film during the process of further forming the organic thin film in the area partitioned by the bank. If the bank is formed using the bank pattern forming method of the present invention, the bank has a good liquid-repellent effect and is less likely to leave residue on the substrate or other layers on the substrate, making it possible to produce a clean organic thin film.

Here, in the case of an organic electroluminescent device, examples of the other layers that can be formed on the substrate 11 include layers such as an anode, a cathode, a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, a blocking layer, and a light emitting layer. When the bank pattern forming method of the present invention is used for an organic electroluminescent device, the other layer is particularly preferably a hole injection layer of an organic electroluminescent device. The other layer is composed 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 may further contain, if desired, one or more of a crosslinking agent (component (E)), a compound having two or more ethylenic polymerizable groups (component (F)), a compound having two or more functional groups that form a covalent bond with an acid (component (G)), and other additives.
Component (A): an alkali-soluble resin having an amide group,
(C) component: solvent,
Component (D): Photosensitizer.

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

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, but is, for example, 1% by mass to 80% by mass, or, for example, 5% by mass to 60% by mass, or 10% by mass to 50% by mass. Here, the solids refers to the total components of the photosensitive resin composition excluding component (C).

The method for preparing the first photosensitive resin composition used in the present invention is not particularly limited, but examples of the preparation method include a method in which component (A) (specific polymer) is dissolved in component (C), and this solution is mixed with component (D) a photosensitizer, if necessary component (E) a crosslinking agent, component (F) a compound having two or more ethylenic polymerizable groups, and component (G) a compound having two or more functional groups that form covalent bonds with an acid in a predetermined ratio to prepare a homogeneous solution, or a method in which other additives are further added and mixed at an appropriate stage of this preparation method as necessary.

When preparing the first 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 is. In this case, when components (A), (D), and, if necessary, components (E), (F), and (G), are added to prepare a homogeneous solution, component (C) may be added for the purpose of adjusting the concentration. In this case, the component (C) used in the process of forming the specific copolymer and the component (C) used for adjusting the concentration when preparing the first photosensitive resin composition may be the same or different.

It is preferable to use the prepared solution of the first photosensitive resin composition after filtering it using a filter with 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 may further contain, if desired, one or more of a crosslinking agent (e), a compound having two or more ethylenic polymerizable groups (f), a compound having two or more functional groups that form a covalent bond with an acid (g), and other additives.
Component (a): an alkali-soluble resin,
Component (b): a polymer having a liquid repellent group (b1),
(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 (b) per 100 parts by mass of component (a), and these components being dissolved in component (c).
[2]: A second photosensitive resin composition comprising, per 100 parts by mass of the component (a), 0.1 to 20 parts by mass of the component (b) and 5 to 100 parts by mass of the component (d), which are dissolved in the component (c), and further comprising the component (d-1).
[3]: A second photosensitive resin composition comprising 0.1 to 20 parts by mass of a component (b) and 5 to 100 parts by mass of a component (d) per 100 parts by mass of the component (a), with these components dissolved in a component (c), and further comprising 1 to 50 parts by mass of a crosslinking agent as a component (e) per 100 parts by mass of the total of the components (a) and (b), wherein the component (d) is a component (d-1).
[4]: A second photosensitive resin composition comprising: 0.1 to 20 parts by mass of the component (b) per 100 parts by mass of the component (a); 5 to 200 parts by mass of the component (f) per 100 parts by mass of the total of the components (a) and (b); and 0.1 to 30 parts by mass of the component (d) per 100 parts by mass of the total of the components (a), (b), and (f), dissolved in the component (c); and wherein the component (d) is the component (d-2).
[5]: A second photosensitive resin composition constituted by a component (a) containing a liquid repellent group (b1) and in which 5 parts by mass to 30 parts by mass of polymerization units having a liquid repellent group (b1) are contained in 100 parts by mass of component (a) not including component (b).

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, or, for example, 5% by mass to 60% by mass, or 10% by mass to 50% by mass. Here, the solids refers to all the components of the second photosensitive resin composition excluding component (c).

The method for preparing the second photosensitive resin composition used in the present invention is not particularly limited, but examples of the preparation method include a method in which component (b) is dissolved in component (c), and the solution is mixed with component (a) of an alkali-soluble resin, component (d) of a photosensitizer, and optionally component (e) of a crosslinking agent, component (f) of a compound having two or more ethylenic polymerizable groups, and component (g) of a compound having two or more functional groups that form covalent bonds with an acid in a predetermined ratio to prepare a homogeneous solution, or a method in which other additives are further added and mixed at an appropriate stage of this preparation method 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 the (c) component can be used as it is, and in this case, when the (a), (d) components, and if necessary the (e), (f), and (g) components are added to the solution of this (b) component to prepare a uniform solution as in the preparation of the first photosensitive resin composition, the (c) component may be added for the purpose of adjusting the concentration. At this time, the (c) component used in the process of forming the specific copolymer and the (c) component used for adjusting the concentration in the preparation of the second photosensitive resin composition may be the same or different.

It is preferable to use the prepared solution of the second photosensitive resin composition after filtering it using a filter with 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 can be applied onto a semiconductor substrate (e.g., a silicon/silicon dioxide coated substrate, a silicon nitride substrate, a substrate coated with a metal (e.g., aluminum, molybdenum, chromium), a glass substrate, a quartz substrate, an ITO substrate, etc.) by spin coating, flow coating, roll coating, slit coating, spin coating followed by slit coating, inkjet coating, or the like, and then pre-dried on a hot plate or in an oven, etc., to form a coating film. The coating film is then heat-treated to form a photosensitive resin film as an underlayer film.

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

The 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, or, for example, 0.3 μm to 8 μm.

<Coated Film and Cured Film as Resist Film>
The second photosensitive resin composition used in the present invention can be applied onto the underlayer film obtained above by spin coating, flow coating, roll coating, slit coating, spin coating followed by slit coating, inkjet coating, or the like, and then pre-dried on a hot plate or in an oven, etc., to form a coating film. Then, the coating film is heat-treated to form a photosensitive resin film as a resist film.

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

The thickness of the photosensitive resin film formed from the second photosensitive resin composition is, for example, 0.1 μm to 30 μm, or, for example, 0.2 μm to 10 μm, or, for example, 0.3 μm to 8 μm.

A mask having a predetermined pattern is attached to the coating of the underlayer film and the resist film on the underlayer film obtained above, and light such as ultraviolet light is irradiated and developed with an alkaline developer, whereby either the exposed or unexposed areas are washed out depending on the material composition, and the remaining patterned film is heated at 80°C to 140°C for 0.5 to 10 minutes as necessary to obtain a sharp relief pattern on the end faces.

Examples of the alkaline developer that can be used include aqueous solutions of alkali metal hydroxides such as potassium carbonate, sodium carbonate, potassium hydroxide, and sodium hydroxide, aqueous solutions of quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline, and aqueous solutions of amines such as ethanolamine, propylamine, and ethylenediamine. Furthermore, surfactants and the like can be added to these developers.

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

The development method can be any of the following: puddle method, dipping method, and swing immersion method. The development 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, and then air-dried with compressed air or compressed nitrogen or by spinning to remove moisture from the substrate and obtain a patterned film.

Then, the patterned film is post-baked for thermal curing, specifically by heating it using a hot plate, oven, etc., to obtain a film that has excellent heat resistance, transparency, flattening properties, low water absorption, chemical resistance, etc., and has a good relief pattern.

Post-baking is generally done by heating the film at a temperature selected from the range of 140°C to 270°C for 5 to 30 minutes on a hot plate or 30 to 90 minutes in an oven.

Thus, this post-baking process makes it possible to obtain a cured film with the desired good pattern shape.

As described above, the method for patterning a cured film can form a liquid-repellent bank pattern that is less likely to leave residues of components of the liquid-repellent resist material in areas other than the bank, and can form a uniform organic thin film within the area partitioned by the bank.

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

The 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 methacrylate TMSSMA: methacryloxypropyl tris(trimethylsiloxy)silane KBM-503: 3-methacryloxypropyl triethoxysilane MAA: methacrylic acid MAAm: methacrylamide HPMA-QD: A compound synthesized by condensation reaction of 1 mol of 4-hydroxyphenyl methacrylate with 1.1 mol of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride AIBN: α,α'-azobisisobutyronitrile QD1: A compound synthesized by the condensation reaction of 1 mol of α,α,α'-tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene with 2 mol of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride. QD2: A compound synthesized by the condensation reaction of 1 mol of 4,4',4"-(3-methyl-1-propanyl-3-ylidene)trisphenol with 2 mol of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride. CST: A styrene polymer (manufactured by Maruzen Petrochemical Co., Ltd.) in which a polymer of 85% hydroxystyrene and 15% styrene and a polymer of 70% hydroxystyrene and 30% styrene are mixed in a ratio of 3:7.
8KQ: 8KQ-2001 (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 Nippon Chemical Epoxy Manufacturing Co., Ltd. (currently Nippon Steel & Sumikin Chemical Co., Ltd.)
CEL-2021P: 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate PGME: propylene glycol monomethyl ether PGMEA: propylene glycol monomethyl ether acetate EL: ethyl lactate CH: cyclohexanone PMA-ST: propylene glycol monomethyl ether acetate dispersed silica sol (manufactured by Nissan Chemical Industries, Ltd.)

<Synthesis Example 1>
3.00 g of MAAm, 2.00 g of HPMA, 5.00 g of MMA, 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) (P1). The obtained acrylic polymer had an Mn of 2,300 and an Mw of 5,500.

<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) (P2). The obtained acrylic polymer had an Mn of 3,000 and an Mw of 6,200.

<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) (P3). The obtained acrylic polymer had an Mn of 3,000 and an Mw of 6,400.

<Synthesis Example 4>
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) (P4). The Mn and Mw of the obtained acrylic polymer were 3,500 and 7,500, respectively.

<Synthesis Example 5>
10.9 g of MAA, 25.5 g of HEMA, 28.7 g of MMA, 35.3 g of CHMI, and 6.0 g of AIBN were dissolved in 159.6 g of PGME and reacted at 80° C. for 20 hours to obtain an acrylic polymer solution (solid concentration: 40% by mass) (P5). The Mn and Mw of the obtained acrylic polymer were 3,800 and 6,700, respectively.

<Synthesis Example 6>
MAA 90.00g, HEMA 225.00g, HPMA 45.00g, MMA
180.00 g of dimethylformamide, 360.00 g of CHMI, and 57.60 g of AIBN were dissolved in 1436.40 g of PGME, and the mixture was reacted at 80° C. for 20 hours to obtain an acrylic polymer solution (solid concentration: 40% by mass) (P6). The obtained acrylic polymer had an Mn of 3,100 and an Mw of 6,100.

<Synthesis Example 7>
HPMA-QD 2.50g, TMSSMA 2.58g, PFHMA 5.26g, MAA 0.70g, CHMI 1.46g, AIBN 0.33g to CH 51.3
g of ethyl acetate and stirred at 110° C. for 20 hours to obtain an acrylic polymer solution (solid content concentration: 20% by mass) (P7). The resulting acrylic polymer had an Mn of 7,200 and an Mw of 11,000.

<Synthesis Example 8>
5.00 g of PFHMA, 3.83 g of KBM-503, 1.51 g of HEMA, and 0.52 g of AIBN were dissolved in 25.32 g of PGME and reacted at 80° C. for 20 hours to obtain an acrylic polymer solution (solid concentration: 30% by mass) (P8). The Mn and Mw of the obtained acrylic polymer were 4,800 and 6,700, respectively.

<Synthesis Example 9>
2.0 g of PFHMA, 5.0 g of HPMA, 3.0 g of CHMI, and 0.5 g of AIBN were dissolved in 24.5 g of PGME and reacted at 80° C. for 20 hours to obtain an acrylic polymer solution (solid content concentration: 30% by mass) (P9). The Mn and Mw of the obtained acrylic polymer were 3,000 and 6,500, respectively.

The components (A), (D), and (E) and the solvent (C) were mixed in the compositions shown in Table 1 to prepare first photosensitive resin compositions for underlayer film materials 1 to 8.

In the same manner, second photosensitive resin compositions of upper layer resist film materials 1 to 5 were prepared with the compositions shown in Table 2. The composition ratios in Tables 1 and 2 represent the ratios in solid content.

[Evaluation 1: Evaluation of pattern shape]
The first photosensitive resin composition of the lower layer material 1 to 8 was applied onto an ITO-glass substrate using a spin coater, and then prebaked on a hot plate at a temperature of 100 ° C. for 120 seconds to form a coating film of the lower layer material with a thickness of 0.2 μm. Next, the second photosensitive resin composition of the upper layer material 1 to 5 was applied onto 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 form a coating film of the upper layer material with a thickness of 1.1 μm. This coating film was irradiated with ultraviolet light having a light intensity of 2.6 mW / cm2 at 365 nm for a certain period of time using a Canon Inc. ultraviolet light irradiation device PLA-600FA through a photomask on which a 50 μm line & space pattern was drawn. Thereafter, the coating film was immersed in a 2.38 mass % or 0.4 mass % tetramethylammonium hydroxide (hereinafter referred to as TMAH) aqueous solution for a predetermined period of time, and then washed with running ultrapure water for 30 seconds. The coating was then post-baked by heating at a temperature of 230° C. for 30 minutes to prepare substrates for Examples 1 to 5 and Comparative Examples 6 to 9. In Comparative Examples 1 to 5, substrates were prepared in the same manner as above, without carrying out the steps of applying and pre-baking the underlayer materials 1 to 5. The state of the line and space patterns thus prepared was observed under an optical microscope. Patterns which had peeled off from the substrate were marked with "X", and patterns which had been formed without peeling were marked with "O". The results are shown in Table 3.

[Evaluation 2: Evaluation of bank contact angle]
The first photosensitive resin composition of the lower layer material 5 was applied onto an ITO-glass substrate using a spin coater, and then prebaked on a hot plate at a temperature of 100° C. for 120 seconds to form a coating film of the lower layer material with a thickness of 0.2 μm. Next, the second photosensitive resin composition of the upper layer material 5 was applied onto 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 form a coating film of the upper layer material with a thickness of 1.1 μm. This coating film was irradiated with ultraviolet light having a light intensity of 2.6 mW/cm2 at 365 nm for a certain period of time using an ultraviolet irradiation device 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 period of time, and then washed with running ultrapure water for 30 seconds. Next, this coating film was post-baked by heating at a temperature of 230° C. for 30 minutes to form a cured film on the ITO-glass substrate of Example 5. In Examples 1 to 4, a cured film consisting of the upper layer material and the lower layer material was formed on the ITO-glass substrate in the same manner as above without exposure to ultraviolet light. In Comparative Example 5, a cured film consisting of only the upper layer material was formed on the ITO-glass substrate in the same manner as above without performing the coating and pre-baking process of the lower layer material 5. In Comparative Examples 1 to 4, a cured film consisting of only the upper layer material was formed on the ITO-glass substrate in the same manner as above without performing the coating and pre-baking process of the lower layer materials 1 to 4 and exposure to ultraviolet light. The contact angle of anisole on this cured film was measured using Drop Master manufactured by Kyowa Interface Science Co., Ltd. The obtained results are shown in Table 3. Evaluation 2 was not performed for Comparative Examples 6 to 9 in which peeling of the pattern occurred in Evaluation 1.

[Evaluation 3: Evaluation of contact angle of exposed part on ITO substrate]
The first photosensitive resin composition of the lower layer material 1 to 4 was applied to an ITO-glass substrate using a spin coater, and then prebaked on a hot plate at a temperature of 100 ° C. for 120 seconds to form a coating film of the lower layer material with a thickness of 0.2 μm. Next, the second photosensitive resin composition of the upper layer material 1 to 4 was applied to 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 form a coating film of the upper layer material with a thickness of 1.1 μm. This coating film was irradiated with ultraviolet light having a light intensity of 2.6 mW / cm2 at 365 nm for a certain period of time using an ultraviolet irradiation device PLA-600FA manufactured by Canon Inc. Thereafter, the coating film was immersed in a 2.38 mass % or 0.4 mass % TMAH aqueous solution for a predetermined period of time, and then washed with running ultrapure water for 30 seconds. The coating was then post-baked by heating at 230° C. for 30 minutes to prepare an ITO-glass substrate from which the coating had been developed and removed in Examples 1 to 4. In Example 5, the coating was developed and removed in the same manner as above without exposure to ultraviolet light.
In Comparative Examples 1 to 4, an ITO-glass substrate was prepared in which the coating film was developed and removed in the same manner as above, without carrying out the steps of coating and pre-baking the lower layer materials 1 to 4. In Comparative Example 5, a cured film consisting of only the upper layer material was formed on the ITO-glass substrate in the same manner as above, without carrying out the steps of coating and pre-baking the lower layer material 5 and exposure to ultraviolet light. The contact angle of anisole on this cured film was measured using a Drop Master manufactured by Kyowa Interface Science Co., Ltd. The obtained results are shown in Table 3. Evaluation 3 was not carried out for Comparative Examples 6 to 9 in which peeling of the pattern occurred in Evaluation 1.

As shown in Table 3, Examples 1 to 5, which used an underlayer material, all had smaller contact angles at the openings and better lyophilicity than Comparative Examples 1 to 5, which did not use an underlayer material. Furthermore, in Example 3, which used an underlayer material, no residue was observed in the spaces of the line and space pattern in Evaluation 1, and a good pattern was obtained, whereas in Comparative Example 3, which did not use an underlayer material, particulate residue was observed in the spaces. Furthermore, in Comparative Examples 6 to 9, which used a hydrophilic resin that did not contain amide groups as the underlayer material, the pattern peeled off during development in Evaluation 1, and did not remain on the substrate.

Claims (23)

A method for forming a bank and an area defined by the bank on a substrate, the method comprising the steps of:
an underlayer film forming step of applying a first photosensitive resin composition containing the following components (A), (C) and (D) directly onto a substrate or via another layer to provide an underlayer film;
a resist film forming step of coating a second photosensitive resin composition containing the following components (a), (b), (c) and (d) on the underlayer film to provide a resist film;
a bank forming step of forming a bank by exposing and developing the resist film, and removing the underlying film of the non-bank portion together with the resist film of the non-bank portion during the development process;
Component (A): an alkali-soluble resin having an amide group,
(C) component: solvent,
(D) component: photosensitizer,
Component (a): an alkali-soluble resin,
Component (b): a polymer having a liquid repellent group (b1),
(c) component: solvent,
(d) component: photosensitizer,
The method for forming a bank pattern, wherein the first photosensitive resin composition satisfies the following (Z2) and (Z3):
(Z2): The alkali-soluble resin having an amide group, component (A) , is a copolymer of methacrylamide, 4-hydroxyphenyl methacrylate, and N-cyclohexylmaleimide ;
(Z3): A photoradical generator in which the component (D) is (D-2) and further contains a compound having two or more ethylenic double bonds as the component (F). 2. The method for 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 crosslinking agent which is the component (e);
(z2): The alkali-soluble resin of the component (a) further has a self-crosslinking group, or further has a group reactive with at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, and an amino group;
(z3): A photoradical generator in which the component (d) is (d-2) and further contains a compound having two or more ethylenic double bonds as the component (f);
(z4): A photoacid generator in which the component (d) is (d-3), and further contains, as the component (g), a compound having two or more functional groups that form a covalent bond with the acid generated from (d-3). The method for forming a bank pattern according to claim 1 or 2, wherein component (D) and/or (d) is a quinone diazide compound. The method for forming a bank pattern according to claim 1, wherein component (D) is a quinone diazide compound and further satisfies (Z2). The method for forming a bank pattern according to claim 2, wherein component (d) is a quinone diazide compound and further satisfies either (z1) or (z2). The method for forming a bank pattern according to claim 4, wherein component (D) is diazonaphthoquinone. The method for forming a bank pattern according to claim 5, wherein component (d) is diazonaphthoquinone. 8. The method for forming a bank pattern according to claim 1, wherein the liquid repellent group (b1) is at least one group selected from a fluoroalkyl group having 3 to 10 carbon atoms, a polyfluoroether group, a silyl ether group, and a polysiloxane group represented by the following formula 4:
-(SiR ¹ R ² -O) _n -SiR ¹ R ² R ³ Formula 4
(wherein R ¹ and R ² independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group; R ³ represents a hydrogen atom or an organic group having 1 to 10 carbon atoms; and n represents an integer of 1 to 200.) The method for forming a bank pattern according to any one of claims 1 to 8, wherein the number average molecular weight of the alkali-soluble resin having an amide group of component (A) and/or the alkali-soluble resin of component (a) is 2,000 to 50,000 in terms of polystyrene. The method for forming a bank pattern according to any one of claims 1 to 9, characterized in that it contains 0.1 to 20 parts by mass of component (b) per 100 parts by mass of component (a). The method for forming a bank pattern according to any one of claims 1 to 10, wherein the polymer of component (b) is an acrylic polymer. The method for forming a bank pattern according to claim 11, wherein the number average molecular weight of the acrylic polymer of component (b) is 2,000 to 100,000 in terms of polystyrene. The method for forming a bank pattern according to any one of claims 2 to 12, characterized in that the amount of component (e) is 1 part by mass to 50 parts by mass per 100 parts by mass of the total of components (a) and (b). 14. The method for forming a bank pattern according to claim 1, wherein the component (b) is a polymer further comprising the following (b2):
(b2): at least one group selected from an N-alkoxymethylamide group, a blocked isocyanate group, and a trialkoxysilyl group 15. The method for forming a bank pattern according to claim 1, wherein the component (b) is a polymer further comprising the following (b3):
(b3): at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group, and an amino group A method for forming a bank and an area defined by the bank on a substrate, the method comprising the steps of:
an underlayer film forming step of applying a first photosensitive resin composition containing the following components (A), (C) and (D) directly onto a substrate or via another layer to provide an underlayer film;
a resist film forming step of coating a second photosensitive resin composition containing the following components (a), (c), and (d) on the underlayer film to form a resist film;
a bank forming step of forming a bank by exposing and developing the resist film, and removing the underlying film of the non-bank portion together with the resist film of the non-bank portion during the development process;
Component (A): an alkali-soluble resin having an amide group,
(C) component: solvent,
(D) component: photosensitizer,
Component (a): an alkali-soluble resin having a liquid-repellent group (b1);
(c) component: solvent,
Component (d): Photosensitizer The first photosensitive resin composition according to the present invention satisfies the following (Z2) and (Z3):
(Z2): The alkali-soluble resin having an amide group, component (A) , is a copolymer of methacrylamide, 4-hydroxyphenyl methacrylate, and N-cyclohexylmaleimide ;
(Z3): A photoradical generator in which the component (D) is (D-2) and further contains a compound having two or more ethylenic double bonds as the component (F). The method for forming a bank pattern according to claim 16, characterized in that the polymerized units having a liquid repellent group (b1) account for 5 to 30 parts by mass in 100 parts by mass of component (a). The method for forming a bank pattern according to claim 16 or 17, characterized in that the amount of component (e) is 1 part by mass to 50 parts by mass per 100 parts by mass of component (a). The method for forming a bank pattern according to any one of claims 1 to 18, wherein the other layer is an organic electroluminescent hole injection layer. A bank pattern having banks and areas partitioned by the banks on a substrate,
The bank has, from the substrate side, at least a substrate, an underlayer film made of a first photosensitive resin composition containing at least the following components (A) and (D), and a resist film made of a second photosensitive resin composition containing at least the following components (a), (b) and (d), and an area partitioned by the bank does not have the underlayer film or the resist film,
The first photosensitive resin composition has a bank pattern which satisfies the following (Z2) and (Z3).
Component (A): an alkali-soluble resin having an amide group,
(D) component: photosensitizer,
Component (a): an alkali-soluble resin,
Component (b): a polymer having a liquid repellent group (b1),
Component (d): Photosensitizer (Z2): The alkali-soluble resin having an amide group, which is the component (A), is a copolymer of methacrylamide, 4-hydroxyphenyl methacrylate, and N-cyclohexylmaleimide ;
(Z3): A photoradical generator in which the component (D) is (D-2) and further contains a compound having two or more ethylenic double bonds as the component (F). A display element having the bank pattern according to claim 20. A display element having the bank pattern according to claim 20 as a partition wall for forming an image. A photosensitive resin composition for forming an underlayer film is provided for forming an underlayer film under a resist film with respect to a bank pattern having banks and regions partitioned by the banks on a substrate, the composition comprising:
Contains the following components (A), (C) and (D),
Component (A): an alkali-soluble resin having an amide group,
(C) component: solvent,
(D) component: photosensitizer,
A photosensitive resin composition for forming an underlayer film of a resist film, which satisfies the following (Z2) and (Z3):
(Z2): The alkali-soluble resin having an amide group, component (A) , is a copolymer of methacrylamide, 4-hydroxyphenyl methacrylate, and N-cyclohexylmaleimide ;
(Z3): A photoradical generator in which the component (D) is (D-2) and further contains a compound having two or more ethylenic double bonds as the component (F).